ChemWiki - User contributions [en]

File:ABR MO.jpg

2019-05-20T16:58:05Z

Abr17: Abr17 uploaded a new version of File:ABR MO.jpg

File:ABR MO.jpg

2019-05-20T16:57:24Z

Abr17: Abr17 uploaded a new version of File:ABR MO.jpg

Comp 01190874 ABR

2019-05-20T16:51:36Z

Abr17: /* Molecular Orbital Analysis */

Inorganic Lab 2019

==BH<sub>3</sub>==

===Initial Calculation===

B3LYP/3-21G level

[[File:ABR_BH3_opt_321G_summary.jpg]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
</pre>

===Higher Accuracy Calculation===

B3LYP/6-31G level

[[File:ABR_BH3_opt_631G_dp_summary.jpg]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000012 0.000450 YES
RMS Force 0.000008 0.000300 YES
Maximum Displacement 0.000064 0.001800 YES
RMS Displacement 0.000039 0.001200 YES
</pre>

Total energy for 3-21G calculationː-26.46226371 a.u.

Total energy for 6-31G calculation with D3h symmetryː -26.61532364 a.u.

<pre>
Low frequencies --- -7.5936 -1.5614 -0.0055 0.6514 6.9319 7.1055

Low frequencies --- 1162.9677 1213.1634 1213.1661
</pre>

[[File:ABR_BH3_FREQ.LOG]]

===Vibrational Spectrum===

{| class="wikitable"
|+
|-
|wavenumber (cm<sup>-1</sup> || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A<sub>2</sub>
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|very slight
|bend
|-
|1213
|14
|E'
|very slight
|bend
|-
|2582
|0
|A<sub>1</sub>'
|no
|symmetric stretch
|-
|2716
|126
|E'
|yes
|asymmetric stretch
|-
|2716
|126
|E'
|yes
|asymmetric stretch
|}

[[File:ABR_BH3_spectrum .jpg|700px]]

There are six vibrations for BH<sub>3</sub> and only three peaks in the IR spectrum because some vibrations do not produce an overall change in dipole moment and are therefore not IR active - the symmetric stretch is not IR active and is not seen in the spectrum. Some vibrations are degenerate (ie. have the same energies) and therefore appear as one peak in the spectrum - the two asymmetric stretches appear as one as do the two bends. Therefore only three peaks are seen in the IR spectrum.

<jmol><jmolApplet>
<title>BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_BH3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

===Molecular Orbital Analysis===

[[File:ABR_BH3_MO.jpg]]

Although qualitative MO theory does not give a perfect representation of the real MOs, it creates a good prediction of the real MOs. For this reason, qualitative MO theory is relatively usefull in predicting real MOs, as it gives a decently accurate depiction.

==NH<sub>3</sub>==

B3LYP/6-31G level

[[File:Abr_NH3_opt_631G_summary.png]]

<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>

<pre>
Low frequencies --- -8.5646 -8.5588 -0.0047 0.0454 0.1784 26.4183

Low frequencies --- 1089.7603 1694.1865 1694.1865
</pre>

[[File:ABR_NH3_FREQ.LOG]]

Total energy isː-56.55776873 a.u.

<jmol><jmolApplet>
<title>NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_NH3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

==Association Energies - BH<sub>3</sub>NH<sub>3</sub>==

===BH<sub>3</sub>NH<sub>3</sub>===

B3LYP/6-31G level

[[File:ABR_BH3NH3_opt_631G_summary.png]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000513 0.001800 YES
RMS Displacement 0.000296 0.001200 YES
</pre>

<pre>
Low frequencies --- -0.0010 -0.0010 0.0007 18.4381 27.1658 40.5145

Low frequencies --- 266.4358 632.3947 639.7877
</pre>

[[File:ABR_BH3NH3_FREQ.LOG]]

Total energy isː -83.22468893 a.u.

<jmol><jmolApplet>
<title>BH3NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_BH3NH3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

===Association Energy Calculations===

E(NH<sub>3</sub>)= -56.55776873 a.u.

E(BH<sub>3</sub>)= -26.61532364 a.u.

E(NH<sub>3</sub>BH<sub>3</sub>)=-83.22468893 a.u.

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=-83.22468893-(-56.55776873 + -26.61532364)

ΔE=-0.05159656 a.u. ie. -135.466778599 KJmol<sup>-1</sup>

This is a sensible value for a bond energy (ie. several hundred KJmol<sup>-1</sup>.

A BN covalent bond has a dissociation energy of -389±21 KJmol<sup>-1</sup>. Since the bond strength calculated here is -135.466778599 KJmol<sup>-1</sup>, this dative covalent bond is significantly weaker than the normal covalent BN bond.

==NI<sub>3</sub>==

[[File:ABR_NI3_opt_summary.png]]

<pre>
Maximum Force 0.000002 0.000450 YES
RMS Force 0.000002 0.000300 YES
Maximum Displacement 0.000022 0.001800 YES
RMS Displacement 0.000014 0.001200 YES
</pre>

<pre>
Low frequencies --- -12.5522 -12.5460 -6.0047 -0.0039 0.0191 0.0664
Low frequencies --- 100.9969 100.9977 147.3377
</pre>

[[File:ABR_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_NI3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

Final optimised N-I bond distance: 2.18396 Angstrom.

==Ionic Liquids Mini Project==

Please note that for this section I am aware that my low frequency values are outside the desired range of ± 20-30 cm<sup>-1</sup>. I was unable to reduce these values while working with demonstrators to resolve the problem, and was told mention this in my wiki.

===[N(CH<sub>3</sub>)<sub>4</sub>]+===

[[File:ABR_NCH34_opt_631G_summary.png]]

<pre>
Maximum Force 0.000062 0.000450 YES
RMS Force 0.000025 0.000300 YES
Maximum Displacement 0.000152 0.001800 YES
RMS Displacement 0.000064 0.001200 YES
</pre>

<pre>
Low frequencies --- 0.0002 0.0010 0.0012 35.2347 35.2348 35.2348
Low frequencies --- 218.5716 317.3185 317.3185
</pre>

[[File:ABR_NCH34_FREQ.LOG]]

<jmol><jmolApplet>
<title>N(CH3)4</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_NCH34_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

===[P(CH<sub>3</sub>)<sub>4</sub>]+===

[[File:ABR_PCH34_opt_631G_summary.png]]

<pre>
Low frequencies --- -0.0027 -0.0025 -0.0015 50.8172 50.8172 50.8172
Low frequencies --- 186.8946 211.7454 211.7454
</pre>

<pre>
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>

[[File:ABR_PCH34_FREQ.LOG]]

<jmol><jmolApplet>
<title>P(CH3)4</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_PCH34_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

===Charge Analysis===

Formal charges are a way of estimating the electron distribution of a molecule. In the traditional picture, a formal positive charge on N represents the fact that the N atom has made 4 bonds rather than its preferred 3.

[[File:ABR_PCH34_OPT_631G_charges.png|thumb|NBO charge analysis for [P(CH<sub>3</sub>)<sub>4</sub>]+.]]

[[File:ABR_NCH34_NBO_charges.png|thumb|NBO charge analysis for [N(CH<sub>3</sub>)<sub>4</sub>]+.]]

===Molecular Orbital Analysis===

[[File:ABR_MO.jpg]]

The top MO shown above is a very bonding one, the middle one is intermediate, and the bottom one is mostly antibonding.

The top MO has all constituents in the same phase, and thus there are no nodes. Thus this represents a very bonding orbital. This is MO 6

The middle MO has some antibonding interactions through space but not along bonds, and some bonding interactions through bonds. It is thus intermediate. This is MO 19

The bottom MO has antibonding interactions along bonds, ie. it has nodal planes intersecting the N-C bonds, and thus represents a fairly antibonding MO. This is MO 10.

Comp 01190874 ABR

2019-05-20T16:49:17Z

Abr17: /* Molecular Orbital Analysis */

File:ABR MO.jpg

2019-05-20T16:48:59Z

Abr17:

2019-05-20T16:05:21Z

Abr17:

Comp 01190874 ABR

2019-05-20T16:05:05Z

Abr17: /* Charge Analysis */

Inorganic Lab 2019

==BH<sub>3</sub>==

===Initial Calculation===

B3LYP/3-21G level

[[File:ABR_BH3_opt_321G_summary.jpg]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
</pre>

===Higher Accuracy Calculation===

B3LYP/6-31G level

[[File:ABR_BH3_opt_631G_dp_summary.jpg]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000012 0.000450 YES
RMS Force 0.000008 0.000300 YES
Maximum Displacement 0.000064 0.001800 YES
RMS Displacement 0.000039 0.001200 YES
</pre>

Total energy for 3-21G calculationː-26.46226371 a.u.

Total energy for 6-31G calculation with D3h symmetryː -26.61532364 a.u.

<pre>
Low frequencies --- -7.5936 -1.5614 -0.0055 0.6514 6.9319 7.1055

Low frequencies --- 1162.9677 1213.1634 1213.1661
</pre>

[[File:ABR_BH3_FREQ.LOG]]

===Vibrational Spectrum===

{| class="wikitable"
|+
|-
|wavenumber (cm<sup>-1</sup> || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A<sub>2</sub>
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|very slight
|bend
|-
|1213
|14
|E'
|very slight
|bend
|-
|2582
|0
|A<sub>1</sub>'
|no
|symmetric stretch
|-
|2716
|126
|E'
|yes
|asymmetric stretch
|-
|2716
|126
|E'
|yes
|asymmetric stretch
|}

[[File:ABR_BH3_spectrum .jpg|700px]]

There are six vibrations for BH<sub>3</sub> and only three peaks in the IR spectrum because some vibrations do not produce an overall change in dipole moment and are therefore not IR active - the symmetric stretch is not IR active and is not seen in the spectrum. Some vibrations are degenerate (ie. have the same energies) and therefore appear as one peak in the spectrum - the two asymmetric stretches appear as one as do the two bends. Therefore only three peaks are seen in the IR spectrum.

<jmol><jmolApplet>
<title>BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_BH3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

===Molecular Orbital Analysis===

[[File:ABR_BH3_MO.jpg]]

Are there any significant differences between the real and LCAO MOs?
What does this say about the accuracy and usefulness of qualitative MO theory?

==NH<sub>3</sub>==

B3LYP/6-31G level

[[File:Abr_NH3_opt_631G_summary.png]]

<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>

<pre>
Low frequencies --- -8.5646 -8.5588 -0.0047 0.0454 0.1784 26.4183

Low frequencies --- 1089.7603 1694.1865 1694.1865
</pre>

[[File:ABR_NH3_FREQ.LOG]]

Total energy isː-56.55776873 a.u.

<jmol><jmolApplet>
<title>NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_NH3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

==Association Energies - BH<sub>3</sub>NH<sub>3</sub>==

===BH<sub>3</sub>NH<sub>3</sub>===

B3LYP/6-31G level

[[File:ABR_BH3NH3_opt_631G_summary.png]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000513 0.001800 YES
RMS Displacement 0.000296 0.001200 YES
</pre>

<pre>
Low frequencies --- -0.0010 -0.0010 0.0007 18.4381 27.1658 40.5145

Low frequencies --- 266.4358 632.3947 639.7877
</pre>

[[File:ABR_BH3NH3_FREQ.LOG]]

Total energy isː -83.22468893 a.u.

<jmol><jmolApplet>
<title>BH3NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_BH3NH3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

===Association Energy Calculations===

E(NH<sub>3</sub>)= -56.55776873 a.u.

E(BH<sub>3</sub>)= -26.61532364 a.u.

E(NH<sub>3</sub>BH<sub>3</sub>)=-83.22468893 a.u.

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=-83.22468893-(-56.55776873 + -26.61532364)

ΔE=-0.05159656 a.u. ie. -135.466778599 KJmol<sup>-1</sup>

This is a sensible value for a bond energy (ie. several hundred KJmol<sup>-1</sup>.

Compare to BN covalent (weaker)

Compare to other bonds (ie. weak/strong/medium in the grand scheme of bonds)

Reference!

==NI<sub>3</sub>==

[[File:ABR_NI3_opt_summary.png]]

<pre>
Maximum Force 0.000002 0.000450 YES
RMS Force 0.000002 0.000300 YES
Maximum Displacement 0.000022 0.001800 YES
RMS Displacement 0.000014 0.001200 YES
</pre>

<pre>
Low frequencies --- -12.5522 -12.5460 -6.0047 -0.0039 0.0191 0.0664
Low frequencies --- 100.9969 100.9977 147.3377
</pre>

[[File:ABR_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_NI3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

Final optimised N-I bond distance: 2.18396 Angstrom.

==Ionic Liquids Mini Project==

Please note that for this section I am aware that my low frequency values are outside the desired range of ± 20-30 cm<sup>-1</sup>. I was unable to reduce these values while working with demonstrators to resolve the problem, and was told mention this in my wiki.

===[N(CH<sub>3</sub>)<sub>4</sub>]+===

[[File:ABR_NCH34_opt_631G_summary.png]]

<pre>
Maximum Force 0.000062 0.000450 YES
RMS Force 0.000025 0.000300 YES
Maximum Displacement 0.000152 0.001800 YES
RMS Displacement 0.000064 0.001200 YES
</pre>

<pre>
Low frequencies --- 0.0002 0.0010 0.0012 35.2347 35.2348 35.2348
Low frequencies --- 218.5716 317.3185 317.3185
</pre>

[[File:ABR_NCH34_FREQ.LOG]]

<jmol><jmolApplet>
<title>N(CH3)4</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_NCH34_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

===[P(CH<sub>3</sub>)<sub>4</sub>]+===

[[File:ABR_PCH34_opt_631G_summary.png]]

<pre>
Low frequencies --- -0.0027 -0.0025 -0.0015 50.8172 50.8172 50.8172
Low frequencies --- 186.8946 211.7454 211.7454
</pre>

<pre>
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>

[[File:ABR_PCH34_FREQ.LOG]]

<jmol><jmolApplet>
<title>P(CH3)4</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_PCH34_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

===Charge Analysis===

Compare the charge distribution for these cations, placing images side by side is not sufficient, list and discuss the charges. The key words here are "compare" and "discuss" just presenting the data is not sufficient, you must interpret your results

placed on the nitrogen centre. Based on your results for [N(CH3)4]+, discuss the validity of this traditional description. You should consider the following:
What does the "formal" positive charge on the N represent in the traditional picture?
On what atoms is the positive charge actually located for this cation?

ABR_PCH34_OPT_631G_charges.png

===Molecular Orbital Analysis===

2019-05-20T15:51:44Z

Abr17: /* [P(CH3)4]+ */

Inorganic Lab 2019

==BH<sub>3</sub>==

===Initial Calculation===

B3LYP/3-21G level

[[File:ABR_BH3_opt_321G_summary.jpg]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
</pre>

===Higher Accuracy Calculation===

B3LYP/6-31G level

[[File:ABR_BH3_opt_631G_dp_summary.jpg]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000012 0.000450 YES
RMS Force 0.000008 0.000300 YES
Maximum Displacement 0.000064 0.001800 YES
RMS Displacement 0.000039 0.001200 YES
</pre>

Total energy for 3-21G calculationː-26.46226371 a.u.

Total energy for 6-31G calculation with D3h symmetryː -26.61532364 a.u.

<pre>
Low frequencies --- -7.5936 -1.5614 -0.0055 0.6514 6.9319 7.1055

Low frequencies --- 1162.9677 1213.1634 1213.1661
</pre>

[[File:ABR_BH3_FREQ.LOG]]

===Vibrational Spectrum===

{| class="wikitable"
|+
|-
|wavenumber (cm<sup>-1</sup> || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A<sub>2</sub>
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|very slight
|bend
|-
|1213
|14
|E'
|very slight
|bend
|-
|2582
|0
|A<sub>1</sub>'
|no
|symmetric stretch
|-
|2716
|126
|E'
|yes
|asymmetric stretch
|-
|2716
|126
|E'
|yes
|asymmetric stretch
|}

[[File:ABR_BH3_spectrum .jpg|700px]]

There are six vibrations for BH<sub>3</sub> and only three peaks in the IR spectrum because some vibrations do not produce an overall change in dipole moment and are therefore not IR active - the symmetric stretch is not IR active and is not seen in the spectrum. Some vibrations are degenerate (ie. have the same energies) and therefore appear as one peak in the spectrum - the two asymmetric stretches appear as one as do the two bends. Therefore only three peaks are seen in the IR spectrum.

<jmol><jmolApplet>
<title>BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_BH3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

===Molecular Orbital Analysis===

[[File:ABR_BH3_MO.jpg]]

Are there any significant differences between the real and LCAO MOs?
What does this say about the accuracy and usefulness of qualitative MO theory?

==NH<sub>3</sub>==

B3LYP/6-31G level

[[File:Abr_NH3_opt_631G_summary.png]]

<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>

<pre>
Low frequencies --- -8.5646 -8.5588 -0.0047 0.0454 0.1784 26.4183

Low frequencies --- 1089.7603 1694.1865 1694.1865
</pre>

[[File:ABR_NH3_FREQ.LOG]]

Total energy isː-56.55776873 a.u.

<jmol><jmolApplet>
<title>NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_NH3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

==Association Energies - BH<sub>3</sub>NH<sub>3</sub>==

===BH<sub>3</sub>NH<sub>3</sub>===

B3LYP/6-31G level

[[File:ABR_BH3NH3_opt_631G_summary.png]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000513 0.001800 YES
RMS Displacement 0.000296 0.001200 YES
</pre>

<pre>
Low frequencies --- -0.0010 -0.0010 0.0007 18.4381 27.1658 40.5145

Low frequencies --- 266.4358 632.3947 639.7877
</pre>

[[File:ABR_BH3NH3_FREQ.LOG]]

Total energy isː -83.22468893 a.u.

<jmol><jmolApplet>
<title>BH3NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_BH3NH3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

===Association Energy Calculations===

E(NH<sub>3</sub>)= -56.55776873 a.u.

E(BH<sub>3</sub>)= -26.61532364 a.u.

E(NH<sub>3</sub>BH<sub>3</sub>)=-83.22468893 a.u.

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=-83.22468893-(-56.55776873 + -26.61532364)

ΔE=-0.05159656 a.u. ie. -135.466778599 KJmol<sup>-1</sup>

This is a sensible value for a bond energy (ie. several hundred KJmol<sup>-1</sup>.

Compare to BN covalent (weaker)

Compare to other bonds (ie. weak/strong/medium in the grand scheme of bonds)

Reference!

==NI<sub>3</sub>==

[[File:ABR_NI3_opt_summary.png]]

<pre>
Maximum Force 0.000002 0.000450 YES
RMS Force 0.000002 0.000300 YES
Maximum Displacement 0.000022 0.001800 YES
RMS Displacement 0.000014 0.001200 YES
</pre>

<pre>
Low frequencies --- -12.5522 -12.5460 -6.0047 -0.0039 0.0191 0.0664
Low frequencies --- 100.9969 100.9977 147.3377
</pre>

[[File:ABR_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_NI3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

Final optimised N-I bond distance: 2.18396 Angstrom.

==Ionic Liquids Mini Project==

===[N(CH<sub>3</sub>)<sub>4</sub>]+===

[[File:ABR_NCH34_opt_631G_summary.png]]

<pre>
Maximum Force 0.000062 0.000450 YES
RMS Force 0.000025 0.000300 YES
Maximum Displacement 0.000152 0.001800 YES
RMS Displacement 0.000064 0.001200 YES
</pre>

<pre>
Low frequencies --- 0.0002 0.0010 0.0012 35.2347 35.2348 35.2348
Low frequencies --- 218.5716 317.3185 317.3185
</pre>

===[P(CH<sub>3</sub>)<sub>4</sub>]+===

[[File:ABR_PCH34_opt_631G_summary.png]]

<pre>
Low frequencies --- -0.0027 -0.0025 -0.0015 50.8172 50.8172 50.8172
Low frequencies --- 186.8946 211.7454 211.7454
</pre>

<pre>
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>

File:ABR PCH34 opt 631G summary.png

2019-05-20T15:51:10Z

Abr17:

Comp 01190874 ABR

2019-05-20T15:50:47Z

Abr17: /* [P(CH3)4]+ */

Inorganic Lab 2019

==BH<sub>3</sub>==

===Initial Calculation===

B3LYP/3-21G level

[[File:ABR_BH3_opt_321G_summary.jpg]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000217 0.000450 YES
RMS Force 0.000105 0.000300 YES
Maximum Displacement 0.000919 0.001800 YES
RMS Displacement 0.000441 0.001200 YES
</pre>

===Higher Accuracy Calculation===

B3LYP/6-31G level

[[File:ABR_BH3_opt_631G_dp_summary.jpg]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000012 0.000450 YES
RMS Force 0.000008 0.000300 YES
Maximum Displacement 0.000064 0.001800 YES
RMS Displacement 0.000039 0.001200 YES
</pre>

Total energy for 3-21G calculationː-26.46226371 a.u.

Total energy for 6-31G calculation with D3h symmetryː -26.61532364 a.u.

<pre>
Low frequencies --- -7.5936 -1.5614 -0.0055 0.6514 6.9319 7.1055

Low frequencies --- 1162.9677 1213.1634 1213.1661
</pre>

[[File:ABR_BH3_FREQ.LOG]]

===Vibrational Spectrum===

{| class="wikitable"
|+
|-
|wavenumber (cm<sup>-1</sup> || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A<sub>2</sub>
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|very slight
|bend
|-
|1213
|14
|E'
|very slight
|bend
|-
|2582
|0
|A<sub>1</sub>'
|no
|symmetric stretch
|-
|2716
|126
|E'
|yes
|asymmetric stretch
|-
|2716
|126
|E'
|yes
|asymmetric stretch
|}

[[File:ABR_BH3_spectrum .jpg|700px]]

There are six vibrations for BH<sub>3</sub> and only three peaks in the IR spectrum because some vibrations do not produce an overall change in dipole moment and are therefore not IR active - the symmetric stretch is not IR active and is not seen in the spectrum. Some vibrations are degenerate (ie. have the same energies) and therefore appear as one peak in the spectrum - the two asymmetric stretches appear as one as do the two bends. Therefore only three peaks are seen in the IR spectrum.

<jmol><jmolApplet>
<title>BH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_BH3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

===Molecular Orbital Analysis===

[[File:ABR_BH3_MO.jpg]]

Are there any significant differences between the real and LCAO MOs?
What does this say about the accuracy and usefulness of qualitative MO theory?

==NH<sub>3</sub>==

B3LYP/6-31G level

[[File:Abr_NH3_opt_631G_summary.png]]

<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>

<pre>
Low frequencies --- -8.5646 -8.5588 -0.0047 0.0454 0.1784 26.4183

Low frequencies --- 1089.7603 1694.1865 1694.1865
</pre>

[[File:ABR_NH3_FREQ.LOG]]

Total energy isː-56.55776873 a.u.

<jmol><jmolApplet>
<title>NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_NH3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

==Association Energies - BH<sub>3</sub>NH<sub>3</sub>==

===BH<sub>3</sub>NH<sub>3</sub>===

B3LYP/6-31G level

[[File:ABR_BH3NH3_opt_631G_summary.png]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000513 0.001800 YES
RMS Displacement 0.000296 0.001200 YES
</pre>

<pre>
Low frequencies --- -0.0010 -0.0010 0.0007 18.4381 27.1658 40.5145

Low frequencies --- 266.4358 632.3947 639.7877
</pre>

[[File:ABR_BH3NH3_FREQ.LOG]]

Total energy isː -83.22468893 a.u.

<jmol><jmolApplet>
<title>BH3NH3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_BH3NH3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

===Association Energy Calculations===

E(NH<sub>3</sub>)= -56.55776873 a.u.

E(BH<sub>3</sub>)= -26.61532364 a.u.

E(NH<sub>3</sub>BH<sub>3</sub>)=-83.22468893 a.u.

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)]

ΔE=-83.22468893-(-56.55776873 + -26.61532364)

ΔE=-0.05159656 a.u. ie. -135.466778599 KJmol<sup>-1</sup>

This is a sensible value for a bond energy (ie. several hundred KJmol<sup>-1</sup>.

Compare to BN covalent (weaker)

Compare to other bonds (ie. weak/strong/medium in the grand scheme of bonds)

Reference!

==NI<sub>3</sub>==

[[File:ABR_NI3_opt_summary.png]]

<pre>
Maximum Force 0.000002 0.000450 YES
RMS Force 0.000002 0.000300 YES
Maximum Displacement 0.000022 0.001800 YES
RMS Displacement 0.000014 0.001200 YES
</pre>

<pre>
Low frequencies --- -12.5522 -12.5460 -6.0047 -0.0039 0.0191 0.0664
Low frequencies --- 100.9969 100.9977 147.3377
</pre>

[[File:ABR_NI3_FREQ.LOG]]

<jmol><jmolApplet>
<title>NI3</title>
<color>black</color>
<size>200</size>
<uploadedFileContents>ABR_NI3_FREQ.LOG</uploadedFileContents>
<script>frame 1.1</script>
</jmolApplet></jmol>

Final optimised N-I bond distance: 2.18396 Angstrom.

==Ionic Liquids Mini Project==

===[N(CH<sub>3</sub>)<sub>4</sub>]+===

[[File:ABR_NCH34_opt_631G_summary.png]]

<pre>
Maximum Force 0.000062 0.000450 YES
RMS Force 0.000025 0.000300 YES
Maximum Displacement 0.000152 0.001800 YES
RMS Displacement 0.000064 0.001200 YES
</pre>

<pre>
Low frequencies --- 0.0002 0.0010 0.0012 35.2347 35.2348 35.2348
Low frequencies --- 218.5716 317.3185 317.3185
</pre>

===[P(CH<sub>3</sub>)<sub>4</sub>]+===

Low frequencies --- -0.0027 -0.0025 -0.0015 50.8172 50.8172 50.8172
Low frequencies --- 186.8946 211.7454 211.7454

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

Comp 01190874 ABR

Comp 01190874 ABR

2019-05-20T15:03:07Z

Abr17: /* Association Energy Calculations */