ChemWiki - User contributions [en]

Inorganic:01338507

2019-05-17T16:02:17Z

Jl7617: /* Molecular orbitals LCAO MO diagram */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

'''Charge distribution from NBOs charge analysis:'''

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

'''Charge distribution comparison:'''

<pre>

[N(CH3)4]+ N:-0.295 C: -0.483 H: 0.269

[P(CH3)4]+ P:1.667 C: -1.252 H: 0.298

</pre>

'''Interpret the charge distribution results: '''

Both [N(CH3)4]+ and [P(CH3)4]+ carry +1 charge. In [N(CH3)4]+, all the positive charge sit on H atoms, while in [P(CH3)4]+ positive charge spread on both H and P atoms. This result can be explained by the electronegativity difference of N and P. As N is much more electronegative than P (N: 3.0, P:2.1), N carries negative charge in [N(CH3)4]+ while P carries some positive charge in [P(CH3)4]+.

In [P(CH3)4]+, C is the most electronegative atom while P and H have nearly the same electronegativity.(P: 2.1, H: 2.1, C: 2.5) Positive charge therefore are on P and H.

In [N(CH3)4]+, N is the most electronegative atom (N: 3.0, C: 2.5, H: 2.1), therefore positive charge are all on H atoms. According to traditional formal charge assignment, the positive charge is assigned on N. This represents the electron deficiency of N compared to its normal valence electron numbers. This traditional formal charge assignment ignores the relative electronegativity of all atoms and assumes all electrons are shared evenly between atoms.

===Molecular orbitals LCAO MO diagram===

[[File:Jl MO10.PNG|600px|thumb|left|Molecular orbital 10]]

[[File:Jl MO16.PNG|600px|thumb|left|Molecular orbital 16]]

[[File:Jl MO19.PNG|600px|thumb|left|Molecular orbital 19]]

Inorganic:01338507

2019-05-17T16:01:37Z

Jl7617: /* Mini project: Ionic Liquids: Designer Solvents */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

'''Charge distribution from NBOs charge analysis:'''

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

'''Charge distribution comparison:'''

<pre>

[N(CH3)4]+ N:-0.295 C: -0.483 H: 0.269

[P(CH3)4]+ P:1.667 C: -1.252 H: 0.298

</pre>

'''Interpret the charge distribution results: '''

Both [N(CH3)4]+ and [P(CH3)4]+ carry +1 charge. In [N(CH3)4]+, all the positive charge sit on H atoms, while in [P(CH3)4]+ positive charge spread on both H and P atoms. This result can be explained by the electronegativity difference of N and P. As N is much more electronegative than P (N: 3.0, P:2.1), N carries negative charge in [N(CH3)4]+ while P carries some positive charge in [P(CH3)4]+.

In [P(CH3)4]+, C is the most electronegative atom while P and H have nearly the same electronegativity.(P: 2.1, H: 2.1, C: 2.5) Positive charge therefore are on P and H.

In [N(CH3)4]+, N is the most electronegative atom (N: 3.0, C: 2.5, H: 2.1), therefore positive charge are all on H atoms. According to traditional formal charge assignment, the positive charge is assigned on N. This represents the electron deficiency of N compared to its normal valence electron numbers. This traditional formal charge assignment ignores the relative electronegativity of all atoms and assumes all electrons are shared evenly between atoms.

===Molecular orbitals LCAO MO diagram===

[[File:Jl MO10.PNG|600px|thumb|left|Molecular orbital 10]]

[[File:Jl MO16.PNG|600px|thumb|left|Molecular orbital 10]]

[[File:Jl MO19.PNG|600px|thumb|left|Molecular orbital 10]]

Inorganic:01338507

2019-05-17T16:01:06Z

Jl7617: /* Molecular orbitals LCAO MO diagram */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

'''Charge distribution from NBOs charge analysis:'''

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

'''Charge distribution comparison:'''

<pre>

[N(CH3)4]+ N:-0.295 C: -0.483 H: 0.269

[P(CH3)4]+ P:1.667 C: -1.252 H: 0.298

</pre>

'''Interpret the charge distribution results: '''

Both [N(CH3)4]+ and [P(CH3)4]+ carry +1 charge. In [N(CH3)4]+, all the positive charge sit on H atoms, while in [P(CH3)4]+ positive charge spread on both H and P atoms. This result can be explained by the electronegativity difference of N and P. As N is much more electronegative than P (N: 3.0, P:2.1), N carries negative charge in [N(CH3)4]+ while P carries some positive charge in [P(CH3)4]+.

In [P(CH3)4]+, C is the most electronegative atom while P and H have nearly the same electronegativity.(P: 2.1, H: 2.1, C: 2.5) Positive charge therefore are on P and H.

In [N(CH3)4]+, N is the most electronegative atom (N: 3.0, C: 2.5, H: 2.1), therefore positive charge are all on H atoms. According to traditional formal charge assignment, the positive charge is assigned on N. This represents the electron deficiency of N compared to its normal valence electron numbers. This traditional formal charge assignment ignores the relative electronegativity of all atoms and assumes all electrons are shared evenly between atoms.

===Molecular orbitals LCAO MO diagram===

[[File:Jl MO10.PNG|600px|thumb|left|Molecular orbital 10]]

[[File:Jl MO16.PNG|600px|thumb|left|Molecular orbital 10]]

[[File:Jl MO19.PNG|600px|thumb|left|Molecular orbital 10]]

Inorganic:01338507

2019-05-17T16:00:43Z

Jl7617: /* Molecular orbitals LCAO MO diagram */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

'''Charge distribution from NBOs charge analysis:'''

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

'''Charge distribution comparison:'''

<pre>

[N(CH3)4]+ N:-0.295 C: -0.483 H: 0.269

[P(CH3)4]+ P:1.667 C: -1.252 H: 0.298

</pre>

'''Interpret the charge distribution results: '''

Both [N(CH3)4]+ and [P(CH3)4]+ carry +1 charge. In [N(CH3)4]+, all the positive charge sit on H atoms, while in [P(CH3)4]+ positive charge spread on both H and P atoms. This result can be explained by the electronegativity difference of N and P. As N is much more electronegative than P (N: 3.0, P:2.1), N carries negative charge in [N(CH3)4]+ while P carries some positive charge in [P(CH3)4]+.

In [P(CH3)4]+, C is the most electronegative atom while P and H have nearly the same electronegativity.(P: 2.1, H: 2.1, C: 2.5) Positive charge therefore are on P and H.

In [N(CH3)4]+, N is the most electronegative atom (N: 3.0, C: 2.5, H: 2.1), therefore positive charge are all on H atoms. According to traditional formal charge assignment, the positive charge is assigned on N. This represents the electron deficiency of N compared to its normal valence electron numbers. This traditional formal charge assignment ignores the relative electronegativity of all atoms and assumes all electrons are shared evenly between atoms.

===Molecular orbitals LCAO MO diagram===

[[File:Jl MO10.PNG|500px|thumb|left|Molecular orbital 10]]

[[File:Jl MO16.PNG|500px|thumb|left|Molecular orbital 10]]

[[File:Jl MO19.PNG|500px|thumb|left|Molecular orbital 10]]

Inorganic:01338507

2019-05-17T16:00:32Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

'''Charge distribution from NBOs charge analysis:'''

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

'''Charge distribution comparison:'''

<pre>

[N(CH3)4]+ N:-0.295 C: -0.483 H: 0.269

[P(CH3)4]+ P:1.667 C: -1.252 H: 0.298

</pre>

'''Interpret the charge distribution results: '''

Both [N(CH3)4]+ and [P(CH3)4]+ carry +1 charge. In [N(CH3)4]+, all the positive charge sit on H atoms, while in [P(CH3)4]+ positive charge spread on both H and P atoms. This result can be explained by the electronegativity difference of N and P. As N is much more electronegative than P (N: 3.0, P:2.1), N carries negative charge in [N(CH3)4]+ while P carries some positive charge in [P(CH3)4]+.

In [P(CH3)4]+, C is the most electronegative atom while P and H have nearly the same electronegativity.(P: 2.1, H: 2.1, C: 2.5) Positive charge therefore are on P and H.

In [N(CH3)4]+, N is the most electronegative atom (N: 3.0, C: 2.5, H: 2.1), therefore positive charge are all on H atoms. According to traditional formal charge assignment, the positive charge is assigned on N. This represents the electron deficiency of N compared to its normal valence electron numbers. This traditional formal charge assignment ignores the relative electronegativity of all atoms and assumes all electrons are shared evenly between atoms.

===Molecular orbitals LCAO MO diagram===

[[File:Jl MO10.PNG|500px|thumb|Molecular orbital 10]]

[[File:Jl MO16.PNG|500px|thumb|Molecular orbital 10]]

[[File:Jl MO19.PNG|500px|thumb|Molecular orbital 10]]

Inorganic:01338507

2019-05-17T16:00:10Z

Jl7617: /* Molecular orbitals LCAO MO diagram */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

'''Charge distribution from NBOs charge analysis:'''

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

'''Charge distribution comparison:'''

<pre>

[N(CH3)4]+ N:-0.295 C: -0.483 H: 0.269

[P(CH3)4]+ P:1.667 C: -1.252 H: 0.298

</pre>

'''Interpret the charge distribution results: '''

Both [N(CH3)4]+ and [P(CH3)4]+ carry +1 charge. In [N(CH3)4]+, all the positive charge sit on H atoms, while in [P(CH3)4]+ positive charge spread on both H and P atoms. This result can be explained by the electronegativity difference of N and P. As N is much more electronegative than P (N: 3.0, P:2.1), N carries negative charge in [N(CH3)4]+ while P carries some positive charge in [P(CH3)4]+.

In [P(CH3)4]+, C is the most electronegative atom while P and H have nearly the same electronegativity.(P: 2.1, H: 2.1, C: 2.5) Positive charge therefore are on P and H.

In [N(CH3)4]+, N is the most electronegative atom (N: 3.0, C: 2.5, H: 2.1), therefore positive charge are all on H atoms. According to traditional formal charge assignment, the positive charge is assigned on N. This represents the electron deficiency of N compared to its normal valence electron numbers. This traditional formal charge assignment ignores the relative electronegativity of all atoms and assumes all electrons are shared evenly between atoms.

===Molecular orbitals LCAO MO diagram===

[[File:Jl MO10.PNG|500px|thumb|Molecular orbital 10]]

[[File:Jl MO16.PNG|500px|thumb|Molecular orbital 10]]

[[File:Jl MO19.PNG|500px|thumb|Molecular orbital 10]]

Inorganic:01338507

2019-05-17T15:59:51Z

Jl7617: /* Molecular orbitals LCAO MO diagram */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

'''Charge distribution from NBOs charge analysis:'''

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

'''Charge distribution comparison:'''

<pre>

[N(CH3)4]+ N:-0.295 C: -0.483 H: 0.269

[P(CH3)4]+ P:1.667 C: -1.252 H: 0.298

</pre>

'''Interpret the charge distribution results: '''

Both [N(CH3)4]+ and [P(CH3)4]+ carry +1 charge. In [N(CH3)4]+, all the positive charge sit on H atoms, while in [P(CH3)4]+ positive charge spread on both H and P atoms. This result can be explained by the electronegativity difference of N and P. As N is much more electronegative than P (N: 3.0, P:2.1), N carries negative charge in [N(CH3)4]+ while P carries some positive charge in [P(CH3)4]+.

In [P(CH3)4]+, C is the most electronegative atom while P and H have nearly the same electronegativity.(P: 2.1, H: 2.1, C: 2.5) Positive charge therefore are on P and H.

In [N(CH3)4]+, N is the most electronegative atom (N: 3.0, C: 2.5, H: 2.1), therefore positive charge are all on H atoms. According to traditional formal charge assignment, the positive charge is assigned on N. This represents the electron deficiency of N compared to its normal valence electron numbers. This traditional formal charge assignment ignores the relative electronegativity of all atoms and assumes all electrons are shared evenly between atoms.

===Molecular orbitals LCAO MO diagram===

[[File:Jl MO10.PNG|300px|thumb|Molecular orbital 10]]

[[File:Jl MO16.PNG|300px|thumb|Molecular orbital 10]]

[[File:Jl MO19.PNG|300px|thumb|Molecular orbital 10]]

Inorganic:01338507

2019-05-17T15:59:21Z

Jl7617: /* Molecular orbitals LCAO MO diagram */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

'''Charge distribution from NBOs charge analysis:'''

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

'''Charge distribution comparison:'''

<pre>

[N(CH3)4]+ N:-0.295 C: -0.483 H: 0.269

[P(CH3)4]+ P:1.667 C: -1.252 H: 0.298

</pre>

'''Interpret the charge distribution results: '''

Both [N(CH3)4]+ and [P(CH3)4]+ carry +1 charge. In [N(CH3)4]+, all the positive charge sit on H atoms, while in [P(CH3)4]+ positive charge spread on both H and P atoms. This result can be explained by the electronegativity difference of N and P. As N is much more electronegative than P (N: 3.0, P:2.1), N carries negative charge in [N(CH3)4]+ while P carries some positive charge in [P(CH3)4]+.

In [P(CH3)4]+, C is the most electronegative atom while P and H have nearly the same electronegativity.(P: 2.1, H: 2.1, C: 2.5) Positive charge therefore are on P and H.

In [N(CH3)4]+, N is the most electronegative atom (N: 3.0, C: 2.5, H: 2.1), therefore positive charge are all on H atoms. According to traditional formal charge assignment, the positive charge is assigned on N. This represents the electron deficiency of N compared to its normal valence electron numbers. This traditional formal charge assignment ignores the relative electronegativity of all atoms and assumes all electrons are shared evenly between atoms.

===Molecular orbitals LCAO MO diagram===

[[File:Jl MO10.PNG|thumb|Molecular orbital 10]]

[[File:Jl MO16.PNG|thumb|Molecular orbital 10]]

[[File:Jl MO19.PNG|thumb|Molecular orbital 10]]

File:Jl MO19.PNG

2019-05-17T15:59:12Z

Jl7617:

File:Jl MO16.PNG

2019-05-17T15:58:56Z

Jl7617:

File:Jl MO10.PNG

2019-05-17T15:56:33Z

Jl7617:

Inorganic:01338507

2019-05-17T15:56:08Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

Inorganic:01338507

2019-05-17T15:55:14Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

Inorganic:01338507

2019-05-17T15:55:02Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

Inorganic:01338507

2019-05-17T15:54:52Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

Inorganic:01338507

2019-05-17T15:54:32Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

Inorganic:01338507

2019-05-17T15:54:22Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

Inorganic:01338507

2019-05-17T15:53:22Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

Inorganic:01338507

2019-05-17T09:17:39Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

Inorganic:01338507

2019-05-17T09:16:49Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

'''Charge distribution comparison:'''

<pre>

[N(CH3)4]+ N:-0.295 C: -0.483 H: 0.269

[P(CH3)4]+ P:1.667 C: -1.252 H: 0.298

</pre>

'''Explanation:'''

Inorganic:01338507

2019-05-17T09:16:37Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

'''Charge distribution comparison:'''

<pre>

[N(CH3)4]+ N:-0.295 C: -0.483 H: 0.269

[P(CH3)4]+ P:1.667 C: -1.252 H: 0.298

</pre>

'''Explanation:'''

Inorganic:01338507

2019-05-17T09:15:55Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

<pre>

[N(CH3)4]+ N:-0.295 C: -0.483 H: 0.269

[P(CH3)4]+ P:1.667 C: -1.252 H: 0.298

</pre>

Inorganic:01338507

2019-05-17T09:15:46Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

<pre>

[N(CH3)4]+ N:-0.295 C: -0.483 H: 0.269

[P(CH3)4]+ P:1.667 C: -1.252 H: 0.298

</pre>

Inorganic:01338507

2019-05-16T20:12:39Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|left|Charge distribution on [P(CH3)4]+ molecule]]

Inorganic:01338507

2019-05-16T20:11:37Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|Charge distribution on [P(CH3)4]+ molecule]]

Inorganic:01338507

2019-05-16T20:10:13Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

[[File:Jl7617 N(CH3)4 charge.PNG|left|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|right|Charge distribution on [P(CH3)4]+ molecule]]

Inorganic:01338507

2019-05-16T20:09:25Z

Jl7617: /* Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+ */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

[[File:Jl7617 N(CH3)4 charge.PNG|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|Charge distribution on [P(CH3)4]+ molecule]]

Inorganic:01338507

2019-05-16T20:09:03Z

Jl7617: /* Mini project: Ionic Liquids: Designer Solvents */

==BH3 molecule==

'''Computational level and basis set''': RB3LYP/6-31G level

'''Summary table image''':

[[File:Jl7617sum.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000009 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000034 0.001800 YES
RMS Displacement 0.000017 0.001200 YES
</pre>

'''Frequency analysis log file''' [[Media: Jl7617 JL BH3 FREQ.LOG| BH3_frequency.log]]

'''Low frequencies:'''

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0054 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

'''Jmol image of BH3:'''

<jmol><jmolApplet>
<title>BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>Jl7617 JL BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Information about BH3 vibrations:'''
{| class="wikitable" border="1"
|+ BH3 Vibration Table
! Mode !! Wavenumbers (cm-1) !! Intensity !! Symmetry !! Dipoles (D) !! IR active? !! Types of vibration
|-
| 1 || 1163 || 317 || A2 || 92.55 || YES || out-of-plane bend
|-
| 2 || 1213 || 46 || E' || 14.05 || YES || bend
|-
| 3 || 1213 || 46 || E' || 14.06 || YES || bend
|-
| 4 || 2582 || 0 || A1' || 0.00 || NO || symmetric stretch
|-
| 5 || 2715 || 185 || E' || 126.33 || YES || asymmetric stretch
|-
| 6 || 2715 || 185 || E' || 126.32 || YES || symmetric stretch
|}

'''Snapshot of IR spectrum:'''

[[File:Jl7617 bh3 irspectrum.PNG]]

'''Explanations of IR spectrum:'''

There are six vibration modes of BH3 molecule. However, only four peaks are seen in the IR spectrum. As modes 2 and 3 have same wavenumbers and intensities, peaks of these two modes overlap, therefore overall only 1 peak can be seen for these two modes. So as modes 5 and 6. As for mode 4, there is no change in dipole, therefore IR radiation cannot be absorbed. Mode 4 is IR inactive, no peak can be seen on spectrum.

'''MOs for BH3:'''

[[File:Jl7617 bh3 mo.PNG]] <ref name="Hunt research group tutorial materials" />
<references>
<ref name="Hunt research group tutorial materials">Hunt research group tutorial materials</ref>
</references>

'''Questions about BH3 MOs:'''

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

The LCAO MOs only shows the individual AOs fragments and are only theoretical predictions. Real MOs shows the real electronic structure of the molecule. Real MOs shows the exact amount of each AO contribution.

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

Compared the LCAOs MOs and real MOs, it can be seen that theory predictions correspond to real situation. Therefore, MO theory is useful for making predictions.

==NH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Summary table:'''

[[File:Jl7617 nh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3 FREQ.LOG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000012 0.001800 YES
RMS Displacement 0.000008 0.001200 YES
</pre>

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0128 -0.0024 0.0002 7.0724 8.1020 8.1023
Low frequencies --- 1089.3849 1693.9369 1693.9369
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==NH3BH3 molecule==

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000121 0.000450 YES
RMS Force 0.000057 0.000300 YES
Maximum Displacement 0.000501 0.001800 YES
RMS Displacement 0.000293 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 nh3bh3 sum.PNG]]

'''Frequency File:''' [[Media:JL NH3BH3 FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0252 -0.0033 -0.0009 17.0313 17.0339 36.9288
Low frequencies --- 265.7545 632.2151 639.3376
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NH3BH3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NH3BH3 FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association energies: Ammonia-Borane==

'''energy in AU individual molecules:'''

E(NH3)= -56.55777 a.u.

E(BH3)= -26.61532 a.u.

E(NH3BH3)= -83.22469 a.u.

'''Energy difference:'''

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]= -0.0516 a.u.= -135 kJ/mol

'''Questions:'''

''Based on your energy calculation is the B-N dative bond weak, medium or strong? What comparison have you made to come to this conclusion?''

The bond strength of C-C bond is 346 kJ/mol. Compared to the energy of C-C bond, the bond strength of N-B bond is much smaller that that of C-C. It can be concluded that B-N dative bond is very weak.

==Heavy molecule NI3==

'''Method and Basis set:''' B3LYB/Gen

'''Summary table:'''

[[File:JL7617 NI3 SUM.PNG]]

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000139 0.000450 YES
RMS Force 0.000090 0.000300 YES
Maximum Displacement 0.001129 0.001800 YES
RMS Displacement 0.000796 0.001200 YES
</pre>

'''Frequency file:''' [[Media:JL NI3 FREQ 3333.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -12.7178 -12.7118 -6.4125 -0.0039 0.0189 0.0621
Low frequencies --- 101.0754 101.0761 147.4556
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised NI3 molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL NI3 FREQ 3333.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Optimised N-I distance:''' 2.18370 Å

==Mini project: Ionic Liquids: Designer Solvents==

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000068 0.000450 YES
RMS Force 0.000027 0.000300 YES
Maximum Displacement 0.000151 0.001800 YES
RMS Displacement 0.000067 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 N(CH3)4+ sum.PNG]]

'''Frequency File:''' [[Media:JL -N(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''
<pre>
Low frequencies --- -0.0006 -0.0005 0.0009 22.7128 22.7128 22.7128
Low frequencies --- 190.7452 294.0628 294.0628
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [N(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -N(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

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

'''Method and Basis set:''' B3LYP/6-31G(d,p)

'''Item table:'''

<pre>
Item Value Threshold Converged?
Maximum Force 0.000030 0.000450 YES
RMS Force 0.000012 0.000300 YES
Maximum Displacement 0.000107 0.001800 YES
RMS Displacement 0.000044 0.001200 YES
</pre>

'''Summary table:'''

[[File:Jl7617 P(CH3)4 sum.PNG]]

'''Frequency File:''' [[Media:JL -P(CH3)4-+ FREQ.LOG]]

'''Frequency Table:'''

<pre>
Low frequencies --- -0.0023 0.0023 0.0028 25.3058 25.3058 25.3058
Low frequencies --- 161.2512 195.7467 195.7467
</pre>

'''Image:'''

<jmol><jmolApplet>
<title>optimised [P(CH3)4]+ molecule</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>JL -P(CH3)4-+ FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Compare charge distribution of [N(CH3)4]+ and [P(CH3)4]+===

[[File:Jl7617 N(CH3)4 charge.PNG|thumb|Charge distribution on [N(CH3)4]+ molecule]]

[[File:Jl7617 P(CH3)4 charge.PNG|thumb|Charge distribution on [P(CH3)4]+ molecule]]

File:Jl7617 P(CH3)4 charge.PNG

2019-05-16T20:08:46Z

Jl7617:

File:Jl7617 N(CH3)4 charge.PNG

2019-05-16T20:06:03Z

Jl7617:

Inorganic:01338507

2019-05-16T19:32:07Z

Jl7617: /* Mini project: Ionic Liquids: Designer Solvents */

Inorganic:01338507

2019-05-16T19:28:04Z

Jl7617: /* [N(CH3)4]+ */

Inorganic:01338507

2019-05-16T19:27:32Z

Jl7617: /* [N(CH3)4]+ */

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

2019-05-16T19:25:44Z

Jl7617:

File:Jl7617 P(CH3)4 sum.PNG

2019-05-16T19:24:23Z

Jl7617:

Inorganic:01338507

2019-05-16T19:17:01Z

Jl7617: /* [N(CH3)4]+ */

Inorganic:01338507

2019-05-16T19:16:40Z

Jl7617: /* Mini project: Ionic Liquids: Designer Solvents */

Inorganic:01338507

2019-05-16T15:40:40Z

Jl7617: /* [N(CH3)4]+ */

File:JL -N(CH3)4-+ FREQ.LOG

2019-05-16T15:38:31Z

Jl7617:

File:Jl7617 N(CH3)4+ sum.PNG

2019-05-16T15:35:04Z

Jl7617:

Inorganic:01338507

2019-05-16T15:05:59Z

Jl7617: /* [N(CH3)4]+ */

Inorganic:01338507

2019-05-16T15:05:28Z

Jl7617: /* Heavy molecule NI3 */

Inorganic:01338507

2019-05-16T14:51:52Z

Jl7617: /* Heavy molecule NI3 */

Inorganic:01338507

2019-05-16T14:51:28Z

Jl7617: /* Heavy molecule NI3 */

Inorganic:01338507

2019-05-16T14:51:06Z

Jl7617: /* Association energies: Ammonia-Borane */

Inorganic:01338507

2019-05-16T14:50:41Z

Jl7617: /* Association energies: Ammonia-Borane */

Inorganic:01338507

2019-05-16T14:43:33Z

Jl7617: /* Heavy molecule NI3 */

File:JL7617 NI3 SUM.PNG

2019-05-16T14:43:14Z

Jl7617:

Inorganic:01338507

2019-05-16T14:41:14Z

Jl7617: /* NH3 molecule */

File:JL NH3BH3 FREQ.LOG

2019-05-16T14:40:13Z

Jl7617: