ChemWiki - User contributions [en]

MD5317

2019-05-10T16:16:58Z

Md5317: /* [P(CH3)4]+ and [N(CH3)4]+ Charge Distribution */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!wavenumber (cm-1)
!Intensity (arbitary units)
!Symmetry
!IR Active?
!Type
|-
|1163
|93
|A''2
|yes
|out-of-plane-bend
|-
|1213
|14
|E'
|Slightly
|In-plane-bend
|-
|1213
|14
|E'
|Slight
|In-plane-bend
|-
|2582
|0
|A'1
|No
|Totally Symmetric Stretch
|-
|2716
|126
|E'
|yes
|Asymmetric Stretch
|-
|2716
|126
|E'
|yes
|Asymetric Stretch
|}

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/7/76/NH3BH3_OPTIMISATION.LOG]]

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/NH3BH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/MONALY_NH3BH3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/5/5f/MD5317_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/4/4f/-N%28CH3%294-%2B_OPT_631G_DP.LOG]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e8/-N%28CH3%294-%2B_OPT_631G_DP_FREQ.LOG]]

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/3/3c/-P%28CH3%294-%2B_OPT_631G_DP.LOG]]

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c0/-P%28CH3%294-%2B_FREQ.LOG]]

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only having 5 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram 2.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:MO 20 Diagram 2.png

2019-05-10T16:14:10Z

Md5317:

MD5317

2019-05-10T16:13:30Z

Md5317: /* [N(CH3)4]+ Valence MOs */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!wavenumber (cm-1)
!Intensity (arbitary units)
!Symmetry
!IR Active?
!Type
|-
|1163
|93
|A''2
|yes
|out-of-plane-bend
|-
|1213
|14
|E'
|Slightly
|In-plane-bend
|-
|1213
|14
|E'
|Slight
|In-plane-bend
|-
|2582
|0
|A'1
|No
|Totally Symmetric Stretch
|-
|2716
|126
|E'
|yes
|Asymmetric Stretch
|-
|2716
|126
|E'
|yes
|Asymetric Stretch
|}

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/7/76/NH3BH3_OPTIMISATION.LOG]]

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/NH3BH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/MONALY_NH3BH3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/5/5f/MD5317_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/4/4f/-N%28CH3%294-%2B_OPT_631G_DP.LOG]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e8/-N%28CH3%294-%2B_OPT_631G_DP_FREQ.LOG]]

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/3/3c/-P%28CH3%294-%2B_OPT_631G_DP.LOG]]

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c0/-P%28CH3%294-%2B_FREQ.LOG]]

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram 2.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

MD5317

2019-05-10T16:07:47Z

Md5317: /* Frequency Analysis6-31G(d,p) BH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!wavenumber (cm-1)
!Intensity (arbitary units)
!Symmetry
!IR Active?
!Type
|-
|1163
|93
|A''2
|yes
|out-of-plane-bend
|-
|1213
|14
|E'
|Slightly
|In-plane-bend
|-
|1213
|14
|E'
|Slight
|In-plane-bend
|-
|2582
|0
|A'1
|No
|Totally Symmetric Stretch
|-
|2716
|126
|E'
|yes
|Asymmetric Stretch
|-
|2716
|126
|E'
|yes
|Asymetric Stretch
|}

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/7/76/NH3BH3_OPTIMISATION.LOG]]

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/NH3BH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/MONALY_NH3BH3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/5/5f/MD5317_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/4/4f/-N%28CH3%294-%2B_OPT_631G_DP.LOG]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e8/-N%28CH3%294-%2B_OPT_631G_DP_FREQ.LOG]]

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/3/3c/-P%28CH3%294-%2B_OPT_631G_DP.LOG]]

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c0/-P%28CH3%294-%2B_FREQ.LOG]]

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

MD5317

2019-05-10T16:07:28Z

Md5317: /* Frequency Analysis6-31G(d,p) BH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!wavenumber (cm-1)
!Intensity (arbitary units)
!Symmetry
!IR Active?
!Type
|-
|1163
|93
|A''2
|yes
|out-of-plane-bend
|-
|1213
|14
|E'
|Slightly
|In-plane-bend
|-
|1213
|14
|E'
|Slight
|In-plane-bend
|-
|2582
|0
|A'1
|No
|Totally Symmetric Stretch
|-
|2716
|126
|E'
|yes
|Asymmetric Stretch
|-
|2716
|126
|E'
|yes
|Asymetric Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/7/76/NH3BH3_OPTIMISATION.LOG]]

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/NH3BH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/MONALY_NH3BH3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/5/5f/MD5317_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/4/4f/-N%28CH3%294-%2B_OPT_631G_DP.LOG]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e8/-N%28CH3%294-%2B_OPT_631G_DP_FREQ.LOG]]

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/3/3c/-P%28CH3%294-%2B_OPT_631G_DP.LOG]]

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c0/-P%28CH3%294-%2B_FREQ.LOG]]

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

MD5317

2019-05-10T16:00:30Z

Md5317: /* [P(CH3)4]+ Frequency Analysis */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/7/76/NH3BH3_OPTIMISATION.LOG]]

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/NH3BH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/MONALY_NH3BH3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/5/5f/MD5317_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/4/4f/-N%28CH3%294-%2B_OPT_631G_DP.LOG]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e8/-N%28CH3%294-%2B_OPT_631G_DP_FREQ.LOG]]

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/3/3c/-P%28CH3%294-%2B_OPT_631G_DP.LOG]]

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c0/-P%28CH3%294-%2B_FREQ.LOG]]

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:-P(CH3)4-+ FREQ.LOG

2019-05-10T15:59:57Z

Md5317: Md5317 uploaded a new version of File:-P(CH3)4-+ FREQ.LOG

MD5317

2019-05-10T15:59:16Z

Md5317: /* [P(CH3)4]+ Optimisation 631G (d,p) */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/7/76/NH3BH3_OPTIMISATION.LOG]]

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/NH3BH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/MONALY_NH3BH3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/5/5f/MD5317_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/4/4f/-N%28CH3%294-%2B_OPT_631G_DP.LOG]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e8/-N%28CH3%294-%2B_OPT_631G_DP_FREQ.LOG]]

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/3/3c/-P%28CH3%294-%2B_OPT_631G_DP.LOG]]

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:-P(CH3)4-+ OPT 631G DP.LOG

2019-05-10T15:58:32Z

Md5317:

MD5317

2019-05-10T15:58:00Z

Md5317: /* [N(CH3)4]+ Frequency Analysis */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/7/76/NH3BH3_OPTIMISATION.LOG]]

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/NH3BH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/MONALY_NH3BH3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/5/5f/MD5317_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/4/4f/-N%28CH3%294-%2B_OPT_631G_DP.LOG]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e8/-N%28CH3%294-%2B_OPT_631G_DP_FREQ.LOG]]

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:-N(CH3)4-+ OPT 631G DP FREQ.LOG

2019-05-10T15:57:16Z

Md5317: Md5317 uploaded a new version of File:-N(CH3)4-+ OPT 631G DP FREQ.LOG

MD5317

2019-05-10T15:56:51Z

Md5317: /* [N(CH3)4]+ Optimisation 631g(d,p) */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/7/76/NH3BH3_OPTIMISATION.LOG]]

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/NH3BH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/MONALY_NH3BH3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/5/5f/MD5317_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/4/4f/-N%28CH3%294-%2B_OPT_631G_DP.LOG]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:-N(CH3)4-+ OPT 631G DP.LOG

2019-05-10T15:56:18Z

Md5317:

MD5317

2019-05-10T15:55:48Z

Md5317: /* NI3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/7/76/NH3BH3_OPTIMISATION.LOG]]

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/NH3BH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/MONALY_NH3BH3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/5/5f/MD5317_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:MD5317 NI3 FREQ.LOG

2019-05-10T15:55:13Z

Md5317:

MD5317

2019-05-10T15:54:35Z

Md5317: /* Frequency Analysis6-31G(d,p) NH3BH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/7/76/NH3BH3_OPTIMISATION.LOG]]

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/NH3BH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/MONALY_NH3BH3_FREQ.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:MONALY NH3BH3 FREQ.LOG

2019-05-10T15:54:01Z

Md5317: Md5317 uploaded a new version of File:MONALY NH3BH3 FREQ.LOG

MD5317

2019-05-10T15:53:42Z

Md5317: /* B3LYP/B-31G level, NH3BH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/7/76/NH3BH3_OPTIMISATION.LOG]]

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/a/a9/NH3BH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:NH3BH3 OPT 631G DP.LOG

2019-05-10T15:52:52Z

Md5317: Md5317 uploaded a new version of File:NH3BH3 OPT 631G DP.LOG

MD5317

2019-05-10T15:52:23Z

Md5317: /* B3LYP/3-21G level, NH3BH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/7/76/NH3BH3_OPTIMISATION.LOG]]

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:NH3BH3 OPTIMISATION.LOG

2019-05-10T15:51:46Z

Md5317: Md5317 uploaded a new version of File:NH3BH3 OPTIMISATION.LOG

MD5317

2019-05-10T15:51:07Z

Md5317: /* Frequency Analysis6-31G(d,p) NH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/c8/MONALY_NH3_FREQ2.LOG]]

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:MONALY NH3 FREQ2.LOG

2019-05-10T15:50:25Z

Md5317: Md5317 uploaded a new version of File:MONALY NH3 FREQ2.LOG

MD5317

2019-05-10T15:50:06Z

Md5317: /* 6-31G(d,p) NH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/c/ce/NH3_OPT_631G_DP.LOG]]

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:NH3 OPT 631G DP.LOG

2019-05-10T15:49:28Z

Md5317: Md5317 uploaded a new version of File:NH3 OPT 631G DP.LOG

MD5317

2019-05-10T15:49:03Z

Md5317: /* B3LYP/3-21G level */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

[[MD5317|https://wiki.ch.ic.ac.uk/wiki/images/e/e5/NH3_OPT.LOG]]

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:NH3 OPT.LOG

2019-05-10T15:48:17Z

Md5317: Md5317 uploaded a new version of File:NH3 OPT.LOG

MD5317

2019-05-10T15:47:44Z

Md5317: /* Frequency Analysis6-31G(d,p) BH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

[[MD5317 | https://wiki.ch.ic.ac.uk/wiki/images/0/01/MD_BH3_OPT_631G_DP.LOG]]

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:MD BH3 OPT 631G DP.LOG

2019-05-10T15:46:06Z

Md5317:

MD5317

2019-05-10T15:45:15Z

Md5317: /* B3LYP/3-21G level, BH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

MD5317

2019-05-10T15:44:59Z

Md5317: /* B3LYP/3-21G level, BH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG

[[MD5317| https://wiki.ch.ic.ac.uk/wiki/images/1/1a/MD_BH3_OPT.LOG]]

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:MD BH3 OPT.LOG

2019-05-10T15:43:15Z

Md5317: Md5317 uploaded a new version of File:MD BH3 OPT.LOG

MD5317

2019-05-10T15:35:06Z

Md5317:

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.67
|<nowiki>-0.30</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.06</nowiki>
|<nowiki>-0.48</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.30
|0.27
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:MD BH3 OPT.LOG

2019-05-10T15:22:19Z

Md5317: Md5317 uploaded a new version of File:MD BH3 OPT.LOG

File:MO 9 Diagram 2.png

2019-05-10T15:20:22Z

Md5317:

MD5317

2019-05-10T15:19:56Z

Md5317: /* [N(CH3)4]+ Valence MOs */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram 2.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

File:MO 10 Diagram 2.png

2019-05-10T15:15:55Z

Md5317:

MD5317

2019-05-10T15:15:15Z

Md5317: /* [N(CH3)4]+ Valence MOs */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram 2.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

MD5317

2019-05-10T15:11:44Z

Md5317: /* B3LYP/3-21G level, BH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

MD5317

2019-05-10T15:11:06Z

Md5317: /* [N(CH3)4]+ Valence MOs */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 10 is a bonding orbital. There are nodes only at the p-orbitals of the C atoms, the rest of the orbitals are s and belong to the N and H atoms. The p-orbitals are orientated to be in phase with both of the different s-orbitals and as there are no nodes along the bonds this is bonding. Finally, MO 9 is bonding, one node that occurs at the N due to the presence of a p-orbital. Does not have as many antibonding interactions through space either, which makes this the most bonding orbital of the three chosen.

MD5317

2019-05-10T15:04:03Z

Md5317: /* [N(CH3)4]+ Valence MOs */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms. MO 9 is a bonding orbital. There are nodes only at the p-orbitals of the N atom, the rest of the orbitals are s and belong to

MD5317

2019-05-10T15:02:55Z

Md5317: /* [N(CH3)4]+ Valence MOs */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C and N atoms.

MD5317

2019-05-10T15:02:25Z

Md5317: /* [N(CH3)4]+ Valence MOs */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram.png|350px]]

MO 20 is overall a bonding orbital. There are regions where there are anti-bonding interactions occurring through spaces however, overall it is bonding because the nodes are occurring on the p-orbitals of the C atoms.

MD5317

2019-05-10T14:57:29Z

Md5317: /* Frequency Analysis6-31G(d,p) BH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

Mode 4 is not IR active, the stretching motions cancel one another out so that there is no dipole moment hence the vibration is not IR active.

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram.png|350px]]

MO 20 is overall an anti-bonding orbital. There are regions where there are bonding interactions occurring however, overall it is antibonding.

MD5317

2019-05-10T14:55:41Z

Md5317:

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram.png|350px]]

MO 20 is overall an anti-bonding orbital. There are regions where there are bonding interactions occurring however, overall it is antibonding.

MD5317

2019-05-10T14:54:25Z

Md5317: /* [N(CH3)4]+ Valence MOs */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram.png|350px]]

MO 20

MD5317

2019-05-10T14:53:28Z

Md5317: /* B3LYP/6-31G(d,p) level */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram.png|350px]]

MD5317

2019-05-10T14:53:14Z

Md5317: /* Frequency Analysis6-31G(d,p) BH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

The optimisation file is linked [[Media:MONALY_DEPALA_PHUNT_NH3_OPTF_POP.LOG| here]]

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram.png|350px]]

MD5317

2019-05-10T14:53:02Z

Md5317: /* B3LYP/6-31G(d,p) level */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

The optimisation file is linked [[Media:MONALY_DEPALA_PHUNT_NH3_OPTF_POP.LOG| here]]

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|450px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram.png|350px]]

MD5317

2019-05-10T14:52:37Z

Md5317: /* Frequency Analysis6-31G(d,p) BH3 */

== '''BH3''' ==

=== '''B3LYP/3-21G level, BH3''' ===

[[File:bh3_opt.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
Predicted change in Energy=-1.635268D-07
Optimization completed.
-- Stationary point found.

== '''B3LYP/6-31G(d,p) level''' ==

The optimisation file is linked [[Media:MONALY_DEPALA_PHUNT_NH3_OPTF_POP.LOG| here]]

=== '''Frequency Analysis6-31G(d,p) BH3''' ===

[[File:bh3freq.png|250px]]

{| class="wikitable"
|'''Low frequencies'''
|<nowiki>-7.9073</nowiki>
|<nowiki>-1.6385</nowiki>
|<nowiki>-0.0054</nowiki>
|0.6256
|6.5697
|6.7709
|-
|
|1162.9662
|1213.1623
|1213.1650
|
|
|
|}

'''Item Table for Frequency'''

Item Value Threshold Converged?
Maximum Force 0.000014 0.000450 YES
RMS Force 0.000007 0.000300 YES
Maximum Displacement 0.000055 0.001800 YES
RMS Displacement 0.000027 0.001200 YES

<jmol><jmolApplet>
<title>Optimsed BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY BH3 SYM FREQ OPTIMISED2.LOG</uploadedFileContents>
<script>frame 1.4</script>
</jmolApplet></jmol>

{| class="wikitable"
!Mode
!Frequency
!Infrared
!Vibration Type
|-
|1
|1163
|93
|Bend
|-
|2
|1213
|14
|Bend
|-
|3
|1213
|14
|Bend
|-
|4
|2582
|0
|Stretch
|-
|5
|2716
|126
|Stretch
|-
|6
|2716
|126
|Stretch
|}

'''Insert IR Spectrum'''

[[File:monaly IR spectrum.png|250px]]

=== '''Molecular Orbital Diagram For BH3 ''' ===
'''Molecular Shape:'''Trigonal Planar

'''Point Group:'''D3h

'''MO Diagram:'''

[[File:Mo Diagram.png]]

'''Are there any significant differences between the real and LCAO MOs?'''

The pictorial representation of the orbitals shows the individual contributions from each of the orbitals. However, the actual orbitals are more diffuse and shows a rough shape of what we have predicted. Not as clear as to where the electron density is coming from.

'''What does this say about the accuracy and usefulness of qualitative MO theory?'''

MO theory is a good way to make a prediction for the Schrodinger equation solutions of the molecular orbitals. The energy levels of the MOs are predicted in the same order as the MO diagram and the pictorial representations represent the MOs accurately.

== '''Association energies: Ammonia-Borane''' ==

=== '''NH3''' ===

==== '''B3LYP/3-21G level''' ====
[[File:Optimised Summary Table NH3.png]]

Item Value Threshold Converged?
Maximum Force 0.000057 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000145 0.001800 YES
RMS Displacement 0.000096 0.001200 YES
Predicted change in Energy=-1.132404D-08
Optimization completed.
-- Stationary point found.

==== '''6-31G(d,p) NH3''' ====
[[File:B31g NH3 Summary Table.png]]

Item Value Threshold Converged?
Maximum Force 0.000060 0.000450 YES
RMS Force 0.000040 0.000300 YES
Maximum Displacement 0.000369 0.001800 YES
RMS Displacement 0.000162 0.001200 YES
Predicted change in Energy=-2.259209D-08
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3''' ====
[[File:Frequency Analysis NH3.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000056 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000074 0.001200 YES
Predicted change in Energy=-1.302934D-08
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.0125 -0.0063 -0.0022 309.9591 309.9613 369.9004
Low frequencies --- 864.2110 1685.0379 1685.0382

<jmol><jmolApplet>
<title>Optimsed NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3 FREQ2.LOG</uploadedFileContents>
<script>frame 1.8</script>
</jmolApplet></jmol>

=== '''NH3BH3''' ===

==== B3LYP/3-21G level, '''NH3BH3''' ====

[[File:NH3BH3 321G Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000087 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.000361 0.001800 YES
RMS Displacement 0.000193 0.001200 YES
Predicted change in Energy=-5.541366D-08
Optimization completed.
-- Stationary point found.

==== B3LYP/B-31G level, '''NH3BH3''' ====

[[File:NH3BH3 b31g summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000137 0.000450 YES
RMS Force 0.000038 0.000300 YES
Maximum Displacement 0.001014 0.001800 YES
RMS Displacement 0.000224 0.001200 YES
Predicted change in Energy=-1.121241D-07
Optimization completed.
-- Stationary point found.

==== '''Frequency Analysis6-31G(d,p) NH3BH3''' ====
[[File:NH3BH3 frequency analysis summary table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000243 0.000450 YES
RMS Force 0.000054 0.000300 YES
Maximum Displacement 0.001387 0.001800 YES
RMS Displacement 0.000374 0.001200 YES
Predicted change in Energy=-1.934793D-07
Optimization completed.
-- Stationary point found.

Low frequencies --- -0.2081 -0.0609 -0.0066 10.0986 16.5503 16.5595
Low frequencies --- 263.0248 631.3813 638.8710

<jmol><jmolApplet>
<title>Optimsed NH3BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MONALY NH3BH3 FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''Total Energies (au)''' ====

{| class="wikitable"
!Molecule
!Total Energy (au)
|-
|NH3
|<nowiki>-26.61532</nowiki>
|-
|BH3
|<nowiki>-56.55777</nowiki>
|-
|NH3BH3
|<nowiki>-83.22469</nowiki>
|}

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=E((-83.22469)-(-56.55777)+(-26.61532))

ΔE=E(-0.0516)

ΔE=-135 kJ/mol

'''Is the B-N bond weak, medium or strong?'''

== '''NI3''' ==

[[File:NI3 Summary Table.png|250px]]

Item Value Threshold Converged?
Maximum Force 0.000067 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000482 0.001800 YES
RMS Displacement 0.000327 0.001200 YES
Predicted change in Energy=-5.632576D-08
Optimization completed.
-- Stationary point found.

<jmol><jmolApplet>
<title>Optimsed NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>MD5317 OPT.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

== '''Project Section''' ==

=== '''[N(CH3)4]+''' ===

==== '''[N(CH3)4]+ Optimisation 631g(d,p) ''' ====
Item Value Threshold Converged?
Maximum Force 0.000029 0.000450 YES
RMS Force 0.000006 0.000300 YES
Maximum Displacement 0.000772 0.001800 YES
RMS Displacement 0.000300 0.001200 YES
Predicted change in Energy=-1.443532D-08
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 631gdp summary table2.png|250px]]

==== '''[N(CH3)4]+ Frequency Analysis ''' ====
Low frequencies --- 0.0007 0.0007 0.0008 32.3845 32.3845 32.3845
Low frequencies --- 212.7850 313.4724 313.4724

Item Value Threshold Converged?
Maximum Force 0.000082 0.000450 YES
RMS Force 0.000066 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000487 0.001200 YES
Predicted change in Energy=-4.660485D-07
Optimization completed.
-- Stationary point found.

[[File:N(CH3)4 freq summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [N(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-N(CH3)4-+ OPT 631G DP FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

=== '''[P(CH3)4]+''' ===

==== '''[P(CH3)4]+ Optimisation 631G (d,p)''' ====

Item Value Threshold Converged?
Maximum Force 0.000064 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000783 0.001800 YES
RMS Displacement 0.000307 0.001200 YES
Predicted change in Energy=-1.676732D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 631gdp summary table2.png|250px]]

<jmol><jmolApplet>
<title>Optimsed [P(CH3)4]+</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>-P(CH3)4-+ FREQ.LOG</uploadedFileContents>
<script>frame 1.20</script>
</jmolApplet></jmol>

==== '''[P(CH3)4]+ Frequency Analysis''' ====

Low frequencies --- -0.0017 -0.0015 0.0009 50.3540 50.3540 50.3540
Low frequencies --- 186.2688 211.3255 211.3255

Item Value Threshold Converged?
Maximum Force 0.000149 0.000450 YES
RMS Force 0.000084 0.000300 YES
Maximum Displacement 0.000934 0.001800 YES
RMS Displacement 0.000521 0.001200 YES
Predicted change in Energy=-7.780930D-07
Optimization completed.
-- Stationary point found.

[[File:P(CH3)4 freq summary table.png|250px]]

==== '''[P(CH3)4]+ and [N(CH3)4]+ Charge Distribution''' ====

[[File:P(CH3)4 charge distribution.png|250px]] [[File:N(CH3)4 charge distribution.png|260px]]
{| class="wikitable"
!Atom
!'''[P(CH3)4]+'''
!''' [N(CH3)4]+'''
!Comparison
|-
!Heteroatom (P/N)
|1.667
|<nowiki>-0.295</nowiki>
|The electronegativities of N and P are 3.04 and 2.19 respectively, P is on the third row of the PTE and N is on the second row. P having a lower electronegativity, will mean that it can stabilise a positive charge more effectively than a N. Additionally, P is in the third row which means that the atom is more diffuse, the charge density will decrease which further contributes to the stability of the positive charge.
|-
!C
|<nowiki>-1.060</nowiki>
|<nowiki>-0.483</nowiki>
|The electronegativity of C is 2.55. This means that C is more electronegative than P, therefore there will be more electron density on the C in a C-P bond relative to the C in a C-N bond, N is more electronegative than C. However, C will still have a negative charge in the C-N bond, this is because the N is not very able to hold onto a positive charge therefore, the unit charge has to be spread across all of the atoms.
|-
!H
|0.298
|0.269
|C-H there is not a big difference in these values because electronic effects seen due to electronegativity will drop rapidly with distance away from the atom. This means that the C-H bonds will be very similar.
|}

The formal positive charge on the N atom is a result of the Lewis Structure. The first 3 bond to the methyl groups are a covalent bond, however, due to N only have 3 valence electrons the fourth bond to the methyl group is a dative bond. This means that there is a positive charge to show the difference in the number of electrons that are expected to be seen on a neutral atom as opposed to the number of electrons on the atom in the Lewis structure. Electron deficiency. However, the positive charge is actually spread across the C atoms as well as the N atom, this increases the stability of the cation as the C is less electronegative so can stabilise a positive charge better than a N atom. Additionally, this diagram is just trying to show charges as if they can be localised to an atom however, this is not the case - an MO diagram shows the distribution of a charge in a molecule across different atoms.

==== ''' [N(CH3)4]+ Valence MOs''' ====

'''MO 20'''

[[File:MO20.png|250px]]

[[File:MO 20 Diagram.png|350px]]

'''MO 9'''

[[File:MO 9.png|250px]]

[[File:MO 9 Diagram.png|350px]]

'''MO 10'''

[[File:MO 10.png|250px]]

[[File:MO 10 Diagram.png|350px]]