ChemWiki - User contributions [en]

Jo416i

2018-05-11T15:18:08Z

Jo416: /* Determining the energy of the dative bond */

==Inorganic Computational Lab==

===BH3===

B3LYP/6-31G(d,p)

[[File:Jocd_bh3_sum.PNG]]

<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 file: [[Media:JOCD_BH3_FREQ.LOG| bh3_frequency.log]]

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0055 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

<jmol><jmolApplet>
<title>optimised BH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====Vibrational spectrum for BH3====
{| class="wikitable"
|+
|-
|wavenumber (cm-1 || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A2''
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|slight
|in-plane-bend
|-
|1213
|14
|E'
|slight
|In-plane-bend
|-
|2582
|0
|A1'
|no
|symmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|}

|[[File:Jocd_bh3_ir.svg|300px]]

Only three peaks are seen in the IR spectrum, despite there being 6 vibrations present. 1 of these vibrations (2582 cm-1) is a symmetric stretch, there is therefore no change in overall dipole moment and thus is not seen in the spectra. There are also two pairs of degenerate vibrations which overlap and therefore you only see 1 peak for each pair. This results in 3 peaks seen in the above spectra.

===BH3 Molecular Orbital Diagram===

[[File:JOCD_BH3_MO.png|frame|none|alt=Alt text|BH33 Molecular Orbital Diagram]]<ref>Hunt, T. (2018) Molecular Orbitals in Inorganic Chemistry. [Lecture] Imperial College London, 2018</ref>

Comparisons of the real molecular orbitals versus the molecular orbitals obtained through LCAO shows the power of molecular orbital theory in predicting real, filled orbitals. However, the accuracy and usefulness of MO theory breaks down for the unoccupied orbitals higher up the diagram. There are significant differences in the contributions of the fragment orbitals predicted vs in the 'real' MOs.

==Association energies: Ammonia-Borane==

===NH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000014 0.001800 YES
RMS Displacement 0.000009 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3_FREQ.LOG| NH3_frequency.log]]

<pre>
Low frequencies --- -0.0128 -0.0010 0.0014 7.1032 8.1046 8.1049
Low frequencies --- 1089.3834 1693.9368 1693.9368
</pre>

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===NH3BH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3BH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000320 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3BH3_FREQ.LOG| NH3BH3_frequency.log]]

<pre>
Low frequencies --- -0.0014 -0.0011 -0.0009 16.8481 17.4133 37.2932
Low frequencies --- 265.8219 632.2116 639.3277
</pre>

<jmol><jmolApplet>
<title>optimised NH3bH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Determining the energy of the dative bond===

E(NH3)=-56.5578 a.u. 
E(BH3)=-26.6153 a.u. 
E(NH3BH3)=-83.2247 a.u. 
ΔE=E(NH3BH3)-[E(BH3)+E(NH3)] 
ΔE=-0.0516 a.u. 
'''ΔE=-140 kJ/mol''' (rounded to the nearest 10 kJ/mol) (lit<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref>: 130 kJ/mol)

The dative B-N bond is very weak compared to its covalent equivalents. For instance the H3C-CH3 also shares one electron pair in valence bond theory, however it has a much higher bond strength of roughly 380 KJ/mol<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref>.

==BBr3==

B3LYP/6-31G(d,p)LANL2DZ

[[File:JOCD_BBR3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000008 0.000450 YES
RMS Force 0.000005 0.000300 YES
Maximum Displacement 0.000036 0.001800 YES
RMS Displacement 0.000023 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_BBR3_FREQ.log| BBr3_frequency.log]]

<pre>
Low frequencies --- -0.0137 -0.0064 -0.0046 2.4315 2.4315 4.8421
Low frequencies --- 155.9631 155.9651 267.7052
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BBR3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

{{DOI|10042/202366}}

==Ionic Liquids==

===[N(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_NCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000076 0.000450 YES
RMS Force 0.000017 0.000300 YES
Maximum Displacement 0.001121 0.001800 YES
RMS Displacement 0.000321 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -9.9670 -0.0011 -0.0007 0.0000 3.4930 8.1265
Low frequencies --- 182.5341 288.5524 288.7594
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===[P(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_PCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000146 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.001509 0.001800 YES
RMS Displacement 0.000498 0.001200 YES
</pre>

Frequency file: [[Media:JOCD_PCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -4.5064 0.0014 0.0029 0.0029 10.2391 13.4026
Low frequencies --- 157.0126 192.4654 192.6170
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_PCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====NBO Charge Analysis====

[[File:JOCD_COMB_CHARGE.png|thumb|center|800px|alt= NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]|NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]]

'''[N(CH3)3]+'''

''Atom'': Charge 
''N'': -0.295,
''C'': -0.483,
''H'': 0.269,

'''[P(CH3)3]+'''

''Atom'': Charge 
''P'': 1.667,
''C'': -1.060,
''H'': 0.298,

The charge analysis shows marked differences in the charge distribution between the two structures. In [P(CH3)3]+
, the positive charge is localised significantly on the phosphorous centre. In comparison the nitrogen centre in [N(CH3)3]+ holds a slight negative charge.

The traditional description of [N(CH3)3]+ would suggest a localized, negative charge centered on the nitrogen. As the above analysis shows, this model fails to explain the true nature of the positive charge in the compound. In this case, the positive charge is more delocalised across the entire molecule. Given their natural polarities, nitrogen would be expected to hold a more significant negative partial charge than carbon. This is the behaviour seen in [P(CH3)3]+.

The difference in behaviour is most easily explained by consideration of electronegativities. The difference in electronegativity between P and C is much greater than between N and C, as such the electron density is 'pulled' more strongly towards the P than the N.

This charge delocalisation is pivotal in the low melting point of the ionic liquids (important for their use as solvents). The delocalised charge in the nitrogen compound promotes poor coordination with the anions and thus a lower melting point for the salt. This charge delocalisation (and thus melting point) can be increased by changing the ''R'' groups on the cation, pyridinium ions are examples of groups which result in significant charge delocalisation.

The phosphorous compound, with its more localized charge, likely has a much higher melting point. For something to be useful as an ionic solvent it is ideally needs to have a melting point of <100 °C.

====Molecular Orbital Analysis====

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO10.png
| width1 = 500
| alt1 = Real MO10
| caption1 = Real MO10
| image2 =JOCD_MO10_FO.png
| width2 =500
| alt2 = LCAO MO For MO10
| caption2 = LCAO
}}

The MO above is strongly C-H bonding, with good S-like overlap on the methyl fragments. It is relatively C-N non-bonding with the no nodes sitting directly on the bond.

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO13.png
| width1 = 500
| alt1 = Real MO13
| caption1 = Real MO13
| image2 =JOCD_MO13_FO.png
| width2 =500
| alt2 = LCAO MO For MO13
| caption2 = LCAO
}}

This MO shows both sigma like and pi like bonding character. The p-orbital like fragments at the front show sigma like C-H bonding character as well as pi like C-N bonding character.
The fragments behind the plane have p-like orbitals pointing directly towards the nitrogen center. This results in good overlap with the p-orbital on the nitrogen and results in relatively strong C-N sigma bonding character.

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO19.png
| width1 = 500
| alt1 = Real MO19
| caption1 = Real MO19
| image2 =JOCD_MO19_FO.png
| width2 =500
| alt2 = LCAO MO For MO19
| caption2 = LCAO MO For MO19
}}

MO19 is a completely bonding orbital. This can be seen quickly by all the nodal planes sitting directly on atoms and none on bonds. There is strong overlap between the 'p-like' fragment orbitals and the pz orbital on the nitrogen center. There is also strong C-H bonding character from the overlap of the of the carbon p orbital with the the s orbitals on the hydrogens.

Jo416i

2018-05-11T15:12:06Z

Jo416: /* Molecular Orbital Analysis */

==Inorganic Computational Lab==

===BH3===

B3LYP/6-31G(d,p)

[[File:Jocd_bh3_sum.PNG]]

<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 file: [[Media:JOCD_BH3_FREQ.LOG| bh3_frequency.log]]

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0055 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

<jmol><jmolApplet>
<title>optimised BH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====Vibrational spectrum for BH3====
{| class="wikitable"
|+
|-
|wavenumber (cm-1 || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A2''
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|slight
|in-plane-bend
|-
|1213
|14
|E'
|slight
|In-plane-bend
|-
|2582
|0
|A1'
|no
|symmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|}

|[[File:Jocd_bh3_ir.svg|300px]]

Only three peaks are seen in the IR spectrum, despite there being 6 vibrations present. 1 of these vibrations (2582 cm-1) is a symmetric stretch, there is therefore no change in overall dipole moment and thus is not seen in the spectra. There are also two pairs of degenerate vibrations which overlap and therefore you only see 1 peak for each pair. This results in 3 peaks seen in the above spectra.

===BH3 Molecular Orbital Diagram===

[[File:JOCD_BH3_MO.png|frame|none|alt=Alt text|BH33 Molecular Orbital Diagram]]<ref>Hunt, T. (2018) Molecular Orbitals in Inorganic Chemistry. [Lecture] Imperial College London, 2018</ref>

Comparisons of the real molecular orbitals versus the molecular orbitals obtained through LCAO shows the power of molecular orbital theory in predicting real, filled orbitals. However, the accuracy and usefulness of MO theory breaks down for the unoccupied orbitals higher up the diagram. There are significant differences in the contributions of the fragment orbitals predicted vs in the 'real' MOs.

==Association energies: Ammonia-Borane==

===NH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000014 0.001800 YES
RMS Displacement 0.000009 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3_FREQ.LOG| NH3_frequency.log]]

<pre>
Low frequencies --- -0.0128 -0.0010 0.0014 7.1032 8.1046 8.1049
Low frequencies --- 1089.3834 1693.9368 1693.9368
</pre>

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===NH3BH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3BH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000320 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3BH3_FREQ.LOG| NH3BH3_frequency.log]]

<pre>
Low frequencies --- -0.0014 -0.0011 -0.0009 16.8481 17.4133 37.2932
Low frequencies --- 265.8219 632.2116 639.3277
</pre>

<jmol><jmolApplet>
<title>optimised NH3bH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Determining the energy of the dative bond===

E(NH3)=-56.5578 a.u. 
E(BH3)=-26.6153 a.u. 
E(NH3BH3)=-83.2247 a.u. 
ΔE=E(NH3BH3)-[E(BH3)+E(NH3)] 
ΔE=-0.0516 a.u. 
'''ΔE=-140 KJ/mol''' (lit<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref>: 130 KJ/mol)

The dative B-N bond is very weak compared to its covalent equivalents. For instance the H3C-CH3 also shares one electron pair in valence bond theory, however it has a much higher bond strength of roughly 380 KJ/mol<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref>.

==BBr3==

B3LYP/6-31G(d,p)LANL2DZ

[[File:JOCD_BBR3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000008 0.000450 YES
RMS Force 0.000005 0.000300 YES
Maximum Displacement 0.000036 0.001800 YES
RMS Displacement 0.000023 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_BBR3_FREQ.log| BBr3_frequency.log]]

<pre>
Low frequencies --- -0.0137 -0.0064 -0.0046 2.4315 2.4315 4.8421
Low frequencies --- 155.9631 155.9651 267.7052
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BBR3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

{{DOI|10042/202366}}

==Ionic Liquids==

===[N(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_NCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000076 0.000450 YES
RMS Force 0.000017 0.000300 YES
Maximum Displacement 0.001121 0.001800 YES
RMS Displacement 0.000321 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -9.9670 -0.0011 -0.0007 0.0000 3.4930 8.1265
Low frequencies --- 182.5341 288.5524 288.7594
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===[P(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_PCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000146 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.001509 0.001800 YES
RMS Displacement 0.000498 0.001200 YES
</pre>

Frequency file: [[Media:JOCD_PCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -4.5064 0.0014 0.0029 0.0029 10.2391 13.4026
Low frequencies --- 157.0126 192.4654 192.6170
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_PCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====NBO Charge Analysis====

[[File:JOCD_COMB_CHARGE.png|thumb|center|800px|alt= NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]|NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]]

'''[N(CH3)3]+'''

''Atom'': Charge 
''N'': -0.295,
''C'': -0.483,
''H'': 0.269,

'''[P(CH3)3]+'''

''Atom'': Charge 
''P'': 1.667,
''C'': -1.060,
''H'': 0.298,

The charge analysis shows marked differences in the charge distribution between the two structures. In [P(CH3)3]+
, the positive charge is localised significantly on the phosphorous centre. In comparison the nitrogen centre in [N(CH3)3]+ holds a slight negative charge.

The traditional description of [N(CH3)3]+ would suggest a localized, negative charge centered on the nitrogen. As the above analysis shows, this model fails to explain the true nature of the positive charge in the compound. In this case, the positive charge is more delocalised across the entire molecule. Given their natural polarities, nitrogen would be expected to hold a more significant negative partial charge than carbon. This is the behaviour seen in [P(CH3)3]+.

The difference in behaviour is most easily explained by consideration of electronegativities. The difference in electronegativity between P and C is much greater than between N and C, as such the electron density is 'pulled' more strongly towards the P than the N.

This charge delocalisation is pivotal in the low melting point of the ionic liquids (important for their use as solvents). The delocalised charge in the nitrogen compound promotes poor coordination with the anions and thus a lower melting point for the salt. This charge delocalisation (and thus melting point) can be increased by changing the ''R'' groups on the cation, pyridinium ions are examples of groups which result in significant charge delocalisation.

The phosphorous compound, with its more localized charge, likely has a much higher melting point. For something to be useful as an ionic solvent it is ideally needs to have a melting point of <100 °C.

====Molecular Orbital Analysis====

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO10.png
| width1 = 500
| alt1 = Real MO10
| caption1 = Real MO10
| image2 =JOCD_MO10_FO.png
| width2 =500
| alt2 = LCAO MO For MO10
| caption2 = LCAO
}}

The MO above is strongly C-H bonding, with good S-like overlap on the methyl fragments. It is relatively C-N non-bonding with the no nodes sitting directly on the bond.

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO13.png
| width1 = 500
| alt1 = Real MO13
| caption1 = Real MO13
| image2 =JOCD_MO13_FO.png
| width2 =500
| alt2 = LCAO MO For MO13
| caption2 = LCAO
}}

This MO shows both sigma like and pi like bonding character. The p-orbital like fragments at the front show sigma like C-H bonding character as well as pi like C-N bonding character.
The fragments behind the plane have p-like orbitals pointing directly towards the nitrogen center. This results in good overlap with the p-orbital on the nitrogen and results in relatively strong C-N sigma bonding character.

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO19.png
| width1 = 500
| alt1 = Real MO19
| caption1 = Real MO19
| image2 =JOCD_MO19_FO.png
| width2 =500
| alt2 = LCAO MO For MO19
| caption2 = LCAO MO For MO19
}}

MO19 is a completely bonding orbital. This can be seen quickly by all the nodal planes sitting directly on atoms and none on bonds. There is strong overlap between the 'p-like' fragment orbitals and the pz orbital on the nitrogen center. There is also strong C-H bonding character from the overlap of the of the carbon p orbital with the the s orbitals on the hydrogens.

Jo416i

2018-05-11T15:01:20Z

Jo416: /* Ionic Liquids */

==Inorganic Computational Lab==

===BH3===

B3LYP/6-31G(d,p)

[[File:Jocd_bh3_sum.PNG]]

<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 file: [[Media:JOCD_BH3_FREQ.LOG| bh3_frequency.log]]

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0055 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

<jmol><jmolApplet>
<title>optimised BH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====Vibrational spectrum for BH3====
{| class="wikitable"
|+
|-
|wavenumber (cm-1 || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A2''
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|slight
|in-plane-bend
|-
|1213
|14
|E'
|slight
|In-plane-bend
|-
|2582
|0
|A1'
|no
|symmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|}

|[[File:Jocd_bh3_ir.svg|300px]]

Only three peaks are seen in the IR spectrum, despite there being 6 vibrations present. 1 of these vibrations (2582 cm-1) is a symmetric stretch, there is therefore no change in overall dipole moment and thus is not seen in the spectra. There are also two pairs of degenerate vibrations which overlap and therefore you only see 1 peak for each pair. This results in 3 peaks seen in the above spectra.

===BH3 Molecular Orbital Diagram===

[[File:JOCD_BH3_MO.png|frame|none|alt=Alt text|BH33 Molecular Orbital Diagram]]<ref>Hunt, T. (2018) Molecular Orbitals in Inorganic Chemistry. [Lecture] Imperial College London, 2018</ref>

Comparisons of the real molecular orbitals versus the molecular orbitals obtained through LCAO shows the power of molecular orbital theory in predicting real, filled orbitals. However, the accuracy and usefulness of MO theory breaks down for the unoccupied orbitals higher up the diagram. There are significant differences in the contributions of the fragment orbitals predicted vs in the 'real' MOs.

==Association energies: Ammonia-Borane==

===NH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000014 0.001800 YES
RMS Displacement 0.000009 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3_FREQ.LOG| NH3_frequency.log]]

<pre>
Low frequencies --- -0.0128 -0.0010 0.0014 7.1032 8.1046 8.1049
Low frequencies --- 1089.3834 1693.9368 1693.9368
</pre>

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===NH3BH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3BH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000320 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3BH3_FREQ.LOG| NH3BH3_frequency.log]]

<pre>
Low frequencies --- -0.0014 -0.0011 -0.0009 16.8481 17.4133 37.2932
Low frequencies --- 265.8219 632.2116 639.3277
</pre>

<jmol><jmolApplet>
<title>optimised NH3bH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Determining the energy of the dative bond===

E(NH3)=-56.5578 a.u. 
E(BH3)=-26.6153 a.u. 
E(NH3BH3)=-83.2247 a.u. 
ΔE=E(NH3BH3)-[E(BH3)+E(NH3)] 
ΔE=-0.0516 a.u. 
'''ΔE=-140 KJ/mol''' (lit<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref>: 130 KJ/mol)

The dative B-N bond is very weak compared to its covalent equivalents. For instance the H3C-CH3 also shares one electron pair in valence bond theory, however it has a much higher bond strength of roughly 380 KJ/mol<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref>.

==BBr3==

B3LYP/6-31G(d,p)LANL2DZ

[[File:JOCD_BBR3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000008 0.000450 YES
RMS Force 0.000005 0.000300 YES
Maximum Displacement 0.000036 0.001800 YES
RMS Displacement 0.000023 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_BBR3_FREQ.log| BBr3_frequency.log]]

<pre>
Low frequencies --- -0.0137 -0.0064 -0.0046 2.4315 2.4315 4.8421
Low frequencies --- 155.9631 155.9651 267.7052
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BBR3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

{{DOI|10042/202366}}

==Ionic Liquids==

===[N(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_NCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000076 0.000450 YES
RMS Force 0.000017 0.000300 YES
Maximum Displacement 0.001121 0.001800 YES
RMS Displacement 0.000321 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -9.9670 -0.0011 -0.0007 0.0000 3.4930 8.1265
Low frequencies --- 182.5341 288.5524 288.7594
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===[P(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_PCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000146 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.001509 0.001800 YES
RMS Displacement 0.000498 0.001200 YES
</pre>

Frequency file: [[Media:JOCD_PCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -4.5064 0.0014 0.0029 0.0029 10.2391 13.4026
Low frequencies --- 157.0126 192.4654 192.6170
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_PCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====NBO Charge Analysis====

[[File:JOCD_COMB_CHARGE.png|thumb|center|800px|alt= NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]|NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]]

'''[N(CH3)3]+'''

''Atom'': Charge 
''N'': -0.295,
''C'': -0.483,
''H'': 0.269,

'''[P(CH3)3]+'''

''Atom'': Charge 
''P'': 1.667,
''C'': -1.060,
''H'': 0.298,

The charge analysis shows marked differences in the charge distribution between the two structures. In [P(CH3)3]+
, the positive charge is localised significantly on the phosphorous centre. In comparison the nitrogen centre in [N(CH3)3]+ holds a slight negative charge.

The traditional description of [N(CH3)3]+ would suggest a localized, negative charge centered on the nitrogen. As the above analysis shows, this model fails to explain the true nature of the positive charge in the compound. In this case, the positive charge is more delocalised across the entire molecule. Given their natural polarities, nitrogen would be expected to hold a more significant negative partial charge than carbon. This is the behaviour seen in [P(CH3)3]+.

The difference in behaviour is most easily explained by consideration of electronegativities. The difference in electronegativity between P and C is much greater than between N and C, as such the electron density is 'pulled' more strongly towards the P than the N.

This charge delocalisation is pivotal in the low melting point of the ionic liquids (important for their use as solvents). The delocalised charge in the nitrogen compound promotes poor coordination with the anions and thus a lower melting point for the salt. This charge delocalisation (and thus melting point) can be increased by changing the ''R'' groups on the cation, pyridinium ions are examples of groups which result in significant charge delocalisation.

The phosphorous compound, with its more localized charge, likely has a much higher melting point. For something to be useful as an ionic solvent it is ideally needs to have a melting point of <100 °C.

====Molecular Orbital Analysis====

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO10.png
| width1 = 500
| alt1 = Real MO10
| caption1 = Real MO10
| image2 =JOCD_MO10_FO.png
| width2 =500
| alt2 = LCAO MO For MO10
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO13.png
| width1 = 500
| alt1 = Real MO13
| caption1 = Real MO13
| image2 =JOCD_MO13_FO.png
| width2 =500
| alt2 = LCAO MO For MO13
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO19.png
| width1 = 500
| alt1 = Real MO19
| caption1 = Real MO19
| image2 =JOCD_MO19_FO.png
| width2 =500
| alt2 = LCAO MO For MO19
| caption2 = LCAO MO For MO19
}}

Jo416i

2018-05-11T14:48:56Z

Jo416: /* NBO Charge Analysis */

==Inorganic Computational Lab==

===BH3===

B3LYP/6-31G(d,p)

[[File:Jocd_bh3_sum.PNG]]

<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 file: [[Media:JOCD_BH3_FREQ.LOG| bh3_frequency.log]]

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0055 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

<jmol><jmolApplet>
<title>optimised BH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====Vibrational spectrum for BH3====
{| class="wikitable"
|+
|-
|wavenumber (cm-1 || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A2''
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|slight
|in-plane-bend
|-
|1213
|14
|E'
|slight
|In-plane-bend
|-
|2582
|0
|A1'
|no
|symmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|}

|[[File:Jocd_bh3_ir.svg|300px]]

Only three peaks are seen in the IR spectrum, despite there being 6 vibrations present. 1 of these vibrations (2582 cm-1) is a symmetric stretch, there is therefore no change in overall dipole moment and thus is not seen in the spectra. There are also two pairs of degenerate vibrations which overlap and therefore you only see 1 peak for each pair. This results in 3 peaks seen in the above spectra.

===BH3 Molecular Orbital Diagram===

[[File:JOCD_BH3_MO.png|frame|none|alt=Alt text|BH33 Molecular Orbital Diagram]]<ref>Hunt, T. (2018) Molecular Orbitals in Inorganic Chemistry. [Lecture] Imperial College London, 2018</ref>

Comparisons of the real molecular orbitals versus the molecular orbitals obtained through LCAO shows the power of molecular orbital theory in predicting real, filled orbitals. However, the accuracy and usefulness of MO theory breaks down for the unoccupied orbitals higher up the diagram. There are significant differences in the contributions of the fragment orbitals predicted vs in the 'real' MOs.

==Association energies: Ammonia-Borane==

===NH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000014 0.001800 YES
RMS Displacement 0.000009 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3_FREQ.LOG| NH3_frequency.log]]

<pre>
Low frequencies --- -0.0128 -0.0010 0.0014 7.1032 8.1046 8.1049
Low frequencies --- 1089.3834 1693.9368 1693.9368
</pre>

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===NH3BH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3BH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000320 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3BH3_FREQ.LOG| NH3BH3_frequency.log]]

<pre>
Low frequencies --- -0.0014 -0.0011 -0.0009 16.8481 17.4133 37.2932
Low frequencies --- 265.8219 632.2116 639.3277
</pre>

<jmol><jmolApplet>
<title>optimised NH3bH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Determining the energy of the dative bond===

E(NH3)=-56.5578 a.u. 
E(BH3)=-26.6153 a.u. 
E(NH3BH3)=-83.2247 a.u. 
ΔE=E(NH3BH3)-[E(BH3)+E(NH3)] 
ΔE=-0.0516 a.u. 
'''ΔE=-140 KJ/mol''' (lit<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref>: 130 KJ/mol)

The dative B-N bond is very weak compared to its covalent equivalents. For instance the H3C-CH3 also shares one electron pair in valence bond theory, however it has a much higher bond strength of roughly 380 KJ/mol<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref>.

==BBr3==

B3LYP/6-31G(d,p)LANL2DZ

[[File:JOCD_BBR3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000008 0.000450 YES
RMS Force 0.000005 0.000300 YES
Maximum Displacement 0.000036 0.001800 YES
RMS Displacement 0.000023 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_BBR3_FREQ.log| BBr3_frequency.log]]

<pre>
Low frequencies --- -0.0137 -0.0064 -0.0046 2.4315 2.4315 4.8421
Low frequencies --- 155.9631 155.9651 267.7052
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BBR3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

{{DOI|10042/202366}}

==Ionic Liquids==

===[N(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_NCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000076 0.000450 YES
RMS Force 0.000017 0.000300 YES
Maximum Displacement 0.001121 0.001800 YES
RMS Displacement 0.000321 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -9.9670 -0.0011 -0.0007 0.0000 3.4930 8.1265
Low frequencies --- 182.5341 288.5524 288.7594
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===[P(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_PCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000146 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.001509 0.001800 YES
RMS Displacement 0.000498 0.001200 YES
</pre>

Frequency file: [[Media:JOCD_PCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -4.5064 0.0014 0.0029 0.0029 10.2391 13.4026
Low frequencies --- 157.0126 192.4654 192.6170
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_PCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====NBO Charge Analysis====

[[File:JOCD_COMB_CHARGE.png|thumb|center|800px|alt= NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]|NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]]

'''[N(CH3)3]+'''

''Atom'': Charge 
''N'': -0.295,
''C'': -0.483,
''H'': 0.269,

'''[P(CH3)3]+'''

''Atom'': Charge 
''P'': 1.667,
''C'': -1.060,
''H'': 0.298,

The charge analysis shows marked differences in the charge distribution between the two structures. In [P(CH3)3]+
, the positive charge is localised significantly on the phosphorous centre. In comparison the nitrogen centre in [N(CH3)3]+ holds a slight negative charge.

The traditional description of [N(CH3)3]+ would suggest a localized, negative charge centered on the nitrogen. As the above analysis shows, this model fails to explain the true nature of the positive charge in the compound. In this case, the positive charge is more delocalised across the entire molecule. Given their natural polarities, nitrogen would be expected to hold a more significant negative partial charge than carbon. This is the behaviour seen in [P(CH3)3]+.

The difference in behaviour is most easily explained by consideration of electronegativities. The difference in electronegativity between P and C is much greater than between N and C, as such the electron density is 'pulled' more strongly towards the P than the N.

====Molecular Orbital Analysis====

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO10.png
| width1 = 500
| alt1 = Real MO10
| caption1 = Real MO10
| image2 =JOCD_MO10_FO.png
| width2 =500
| alt2 = LCAO MO For MO10
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO13.png
| width1 = 500
| alt1 = Real MO13
| caption1 = Real MO13
| image2 =JOCD_MO13_FO.png
| width2 =500
| alt2 = LCAO MO For MO13
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO19.png
| width1 = 500
| alt1 = Real MO19
| caption1 = Real MO19
| image2 =JOCD_MO19_FO.png
| width2 =500
| alt2 = LCAO MO For MO19
| caption2 = LCAO MO For MO19
}}

Jo416i

2018-05-11T14:39:20Z

Jo416: /* Determining the energy of the dative bond */

==Inorganic Computational Lab==

===BH3===

B3LYP/6-31G(d,p)

[[File:Jocd_bh3_sum.PNG]]

<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 file: [[Media:JOCD_BH3_FREQ.LOG| bh3_frequency.log]]

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0055 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

<jmol><jmolApplet>
<title>optimised BH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====Vibrational spectrum for BH3====
{| class="wikitable"
|+
|-
|wavenumber (cm-1 || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A2''
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|slight
|in-plane-bend
|-
|1213
|14
|E'
|slight
|In-plane-bend
|-
|2582
|0
|A1'
|no
|symmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|}

|[[File:Jocd_bh3_ir.svg|300px]]

Only three peaks are seen in the IR spectrum, despite there being 6 vibrations present. 1 of these vibrations (2582 cm-1) is a symmetric stretch, there is therefore no change in overall dipole moment and thus is not seen in the spectra. There are also two pairs of degenerate vibrations which overlap and therefore you only see 1 peak for each pair. This results in 3 peaks seen in the above spectra.

===BH3 Molecular Orbital Diagram===

[[File:JOCD_BH3_MO.png|frame|none|alt=Alt text|BH33 Molecular Orbital Diagram]]<ref>Hunt, T. (2018) Molecular Orbitals in Inorganic Chemistry. [Lecture] Imperial College London, 2018</ref>

Comparisons of the real molecular orbitals versus the molecular orbitals obtained through LCAO shows the power of molecular orbital theory in predicting real, filled orbitals. However, the accuracy and usefulness of MO theory breaks down for the unoccupied orbitals higher up the diagram. There are significant differences in the contributions of the fragment orbitals predicted vs in the 'real' MOs.

==Association energies: Ammonia-Borane==

===NH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000014 0.001800 YES
RMS Displacement 0.000009 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3_FREQ.LOG| NH3_frequency.log]]

<pre>
Low frequencies --- -0.0128 -0.0010 0.0014 7.1032 8.1046 8.1049
Low frequencies --- 1089.3834 1693.9368 1693.9368
</pre>

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===NH3BH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3BH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000320 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3BH3_FREQ.LOG| NH3BH3_frequency.log]]

<pre>
Low frequencies --- -0.0014 -0.0011 -0.0009 16.8481 17.4133 37.2932
Low frequencies --- 265.8219 632.2116 639.3277
</pre>

<jmol><jmolApplet>
<title>optimised NH3bH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Determining the energy of the dative bond===

E(NH3)=-56.5578 a.u. 
E(BH3)=-26.6153 a.u. 
E(NH3BH3)=-83.2247 a.u. 
ΔE=E(NH3BH3)-[E(BH3)+E(NH3)] 
ΔE=-0.0516 a.u. 
'''ΔE=-140 KJ/mol''' (lit<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref>: 130 KJ/mol)

The dative B-N bond is very weak compared to its covalent equivalents. For instance the H3C-CH3 also shares one electron pair in valence bond theory, however it has a much higher bond strength of roughly 380 KJ/mol<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref>.

==BBr3==

B3LYP/6-31G(d,p)LANL2DZ

[[File:JOCD_BBR3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000008 0.000450 YES
RMS Force 0.000005 0.000300 YES
Maximum Displacement 0.000036 0.001800 YES
RMS Displacement 0.000023 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_BBR3_FREQ.log| BBr3_frequency.log]]

<pre>
Low frequencies --- -0.0137 -0.0064 -0.0046 2.4315 2.4315 4.8421
Low frequencies --- 155.9631 155.9651 267.7052
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BBR3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

{{DOI|10042/202366}}

==Ionic Liquids==

===[N(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_NCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000076 0.000450 YES
RMS Force 0.000017 0.000300 YES
Maximum Displacement 0.001121 0.001800 YES
RMS Displacement 0.000321 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -9.9670 -0.0011 -0.0007 0.0000 3.4930 8.1265
Low frequencies --- 182.5341 288.5524 288.7594
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===[P(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_PCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000146 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.001509 0.001800 YES
RMS Displacement 0.000498 0.001200 YES
</pre>

Frequency file: [[Media:JOCD_PCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -4.5064 0.0014 0.0029 0.0029 10.2391 13.4026
Low frequencies --- 157.0126 192.4654 192.6170
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_PCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====NBO Charge Analysis====

[[File:JOCD_COMB_CHARGE.png|thumb|center|800px|alt= NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]|NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]]

'''[N(CH3)3]+'''

''Atom'': Charge 
''N'': -0.295,
''C'': -0.483,
''H'': 0.269,

'''[P(CH3)3]+'''

''Atom'': Charge 
''P'': 1.667,
''C'': -1.060,
''H'': 0.298,

The charge analysis shows marked differences in the charge distribution between the two structures. In [P(CH3)3]+
, the positive charge is localised significantly on the phosphorous centre. In comparison the nitrogen centre in [N(CH3)3]+ holds a slight negative charge.

====Molecular Orbital Analysis====

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO10.png
| width1 = 500
| alt1 = Real MO10
| caption1 = Real MO10
| image2 =JOCD_MO10_FO.png
| width2 =500
| alt2 = LCAO MO For MO10
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO13.png
| width1 = 500
| alt1 = Real MO13
| caption1 = Real MO13
| image2 =JOCD_MO13_FO.png
| width2 =500
| alt2 = LCAO MO For MO13
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO19.png
| width1 = 500
| alt1 = Real MO19
| caption1 = Real MO19
| image2 =JOCD_MO19_FO.png
| width2 =500
| alt2 = LCAO MO For MO19
| caption2 = LCAO MO For MO19
}}

Jo416i

2018-05-11T14:09:05Z

Jo416: /* Determining the energy of the dative bond */

==Inorganic Computational Lab==

===BH3===

B3LYP/6-31G(d,p)

[[File:Jocd_bh3_sum.PNG]]

<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 file: [[Media:JOCD_BH3_FREQ.LOG| bh3_frequency.log]]

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0055 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

<jmol><jmolApplet>
<title>optimised BH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====Vibrational spectrum for BH3====
{| class="wikitable"
|+
|-
|wavenumber (cm-1 || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A2''
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|slight
|in-plane-bend
|-
|1213
|14
|E'
|slight
|In-plane-bend
|-
|2582
|0
|A1'
|no
|symmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|}

|[[File:Jocd_bh3_ir.svg|300px]]

Only three peaks are seen in the IR spectrum, despite there being 6 vibrations present. 1 of these vibrations (2582 cm-1) is a symmetric stretch, there is therefore no change in overall dipole moment and thus is not seen in the spectra. There are also two pairs of degenerate vibrations which overlap and therefore you only see 1 peak for each pair. This results in 3 peaks seen in the above spectra.

===BH3 Molecular Orbital Diagram===

[[File:JOCD_BH3_MO.png|frame|none|alt=Alt text|BH33 Molecular Orbital Diagram]]<ref>Hunt, T. (2018) Molecular Orbitals in Inorganic Chemistry. [Lecture] Imperial College London, 2018</ref>

Comparisons of the real molecular orbitals versus the molecular orbitals obtained through LCAO shows the power of molecular orbital theory in predicting real, filled orbitals. However, the accuracy and usefulness of MO theory breaks down for the unoccupied orbitals higher up the diagram. There are significant differences in the contributions of the fragment orbitals predicted vs in the 'real' MOs.

==Association energies: Ammonia-Borane==

===NH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000014 0.001800 YES
RMS Displacement 0.000009 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3_FREQ.LOG| NH3_frequency.log]]

<pre>
Low frequencies --- -0.0128 -0.0010 0.0014 7.1032 8.1046 8.1049
Low frequencies --- 1089.3834 1693.9368 1693.9368
</pre>

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===NH3BH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3BH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000320 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3BH3_FREQ.LOG| NH3BH3_frequency.log]]

<pre>
Low frequencies --- -0.0014 -0.0011 -0.0009 16.8481 17.4133 37.2932
Low frequencies --- 265.8219 632.2116 639.3277
</pre>

<jmol><jmolApplet>
<title>optimised NH3bH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Determining the energy of the dative bond===

E(NH3)=-56.5578 a.u. 
E(BH3)=-26.6153 a.u. 
E(NH3BH3)=-83.2247 a.u. 
ΔE=E(NH3BH3)-[E(BH3)+E(NH3)] 
ΔE=-0.0516 a.u. 
'''ΔE=-140 KJ/mol''' 

In comparison with the P-Al dative bond in Me3P→AlMe3 (87.9 KJ/Mol)<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref> the BN bond is relatively strong.

==BBr3==

B3LYP/6-31G(d,p)LANL2DZ

[[File:JOCD_BBR3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000008 0.000450 YES
RMS Force 0.000005 0.000300 YES
Maximum Displacement 0.000036 0.001800 YES
RMS Displacement 0.000023 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_BBR3_FREQ.log| BBr3_frequency.log]]

<pre>
Low frequencies --- -0.0137 -0.0064 -0.0046 2.4315 2.4315 4.8421
Low frequencies --- 155.9631 155.9651 267.7052
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BBR3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

{{DOI|10042/202366}}

==Ionic Liquids==

===[N(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_NCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000076 0.000450 YES
RMS Force 0.000017 0.000300 YES
Maximum Displacement 0.001121 0.001800 YES
RMS Displacement 0.000321 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -9.9670 -0.0011 -0.0007 0.0000 3.4930 8.1265
Low frequencies --- 182.5341 288.5524 288.7594
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===[P(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_PCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000146 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.001509 0.001800 YES
RMS Displacement 0.000498 0.001200 YES
</pre>

Frequency file: [[Media:JOCD_PCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -4.5064 0.0014 0.0029 0.0029 10.2391 13.4026
Low frequencies --- 157.0126 192.4654 192.6170
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_PCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====NBO Charge Analysis====

[[File:JOCD_COMB_CHARGE.png|thumb|center|800px|alt= NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]|NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]]

'''[N(CH3)3]+'''

''Atom'': Charge 
''N'': -0.295,
''C'': -0.483,
''H'': 0.269,

'''[P(CH3)3]+'''

''Atom'': Charge 
''P'': 1.667,
''C'': -1.060,
''H'': 0.298,

The charge analysis shows marked differences in the charge distribution between the two structures. In [P(CH3)3]+
, the positive charge is localised significantly on the phosphorous centre. In comparison the nitrogen centre in [N(CH3)3]+ holds a slight negative charge.

====Molecular Orbital Analysis====

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO10.png
| width1 = 500
| alt1 = Real MO10
| caption1 = Real MO10
| image2 =JOCD_MO10_FO.png
| width2 =500
| alt2 = LCAO MO For MO10
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO13.png
| width1 = 500
| alt1 = Real MO13
| caption1 = Real MO13
| image2 =JOCD_MO13_FO.png
| width2 =500
| alt2 = LCAO MO For MO13
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO19.png
| width1 = 500
| alt1 = Real MO19
| caption1 = Real MO19
| image2 =JOCD_MO19_FO.png
| width2 =500
| alt2 = LCAO MO For MO19
| caption2 = LCAO MO For MO19
}}

File:JOCD MO19 FO.png

2018-05-11T13:46:31Z

Jo416: Jo416 uploaded a new version of File:JOCD MO19 FO.png

File:JOCD MO10 FO.png

2018-05-11T13:44:35Z

Jo416: Jo416 uploaded a new version of File:JOCD MO10 FO.png

File:JOCD MO19 FO.png

2018-05-11T13:44:19Z

Jo416: Jo416 uploaded a new version of File:JOCD MO19 FO.png

File:JOCD MO19 FO.png

2018-05-11T13:42:40Z

Jo416: Jo416 uploaded a new version of File:JOCD MO19 FO.png

File:JOCD MO13 FO.png

2018-05-11T13:42:25Z

Jo416: Jo416 uploaded a new version of File:JOCD MO13 FO.png

File:JOCD MO10 FO.png

2018-05-11T13:42:11Z

Jo416: Jo416 uploaded a new version of File:JOCD MO10 FO.png

File:JOCD MO13 FO.png

2018-05-11T13:32:19Z

Jo416: Jo416 uploaded a new version of File:JOCD MO13 FO.png

File:JOCD MO13 FO.png

2018-05-11T13:29:59Z

Jo416: Jo416 uploaded a new version of File:JOCD MO13 FO.png

Jo416i

2018-05-11T13:02:03Z

Jo416: /* NBO Charge Analysis */

==Inorganic Computational Lab==

===BH3===

B3LYP/6-31G(d,p)

[[File:Jocd_bh3_sum.PNG]]

<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 file: [[Media:JOCD_BH3_FREQ.LOG| bh3_frequency.log]]

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0055 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

<jmol><jmolApplet>
<title>optimised BH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====Vibrational spectrum for BH3====
{| class="wikitable"
|+
|-
|wavenumber (cm-1 || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A2''
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|slight
|in-plane-bend
|-
|1213
|14
|E'
|slight
|In-plane-bend
|-
|2582
|0
|A1'
|no
|symmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|}

|[[File:Jocd_bh3_ir.svg|300px]]

Only three peaks are seen in the IR spectrum, despite there being 6 vibrations present. 1 of these vibrations (2582 cm-1) is a symmetric stretch, there is therefore no change in overall dipole moment and thus is not seen in the spectra. There are also two pairs of degenerate vibrations which overlap and therefore you only see 1 peak for each pair. This results in 3 peaks seen in the above spectra.

===BH3 Molecular Orbital Diagram===

[[File:JOCD_BH3_MO.png|frame|none|alt=Alt text|BH33 Molecular Orbital Diagram]]<ref>Hunt, T. (2018) Molecular Orbitals in Inorganic Chemistry. [Lecture] Imperial College London, 2018</ref>

Comparisons of the real molecular orbitals versus the molecular orbitals obtained through LCAO shows the power of molecular orbital theory in predicting real, filled orbitals. However, the accuracy and usefulness of MO theory breaks down for the unoccupied orbitals higher up the diagram. There are significant differences in the contributions of the fragment orbitals predicted vs in the 'real' MOs.

==Association energies: Ammonia-Borane==

===NH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000014 0.001800 YES
RMS Displacement 0.000009 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3_FREQ.LOG| NH3_frequency.log]]

<pre>
Low frequencies --- -0.0128 -0.0010 0.0014 7.1032 8.1046 8.1049
Low frequencies --- 1089.3834 1693.9368 1693.9368
</pre>

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===NH3BH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3BH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000320 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3BH3_FREQ.LOG| NH3BH3_frequency.log]]

<pre>
Low frequencies --- -0.0014 -0.0011 -0.0009 16.8481 17.4133 37.2932
Low frequencies --- 265.8219 632.2116 639.3277
</pre>

<jmol><jmolApplet>
<title>optimised NH3bH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Determining the energy of the dative bond===

E(NH3)=-56.5578 a.u.
E(BH3)=-26.6153 a.u.
E(NH3BH3)=-83.2247 a.u.
ΔE=E(NH3BH3)-[E(BH3)+E(NH3)]
ΔE=-0.0516 a.u.
ΔE=-140 KJ/mol

In comparison with the P-Al dative bond in Me3P→AlMe3 (87.9 KJ/Mol)<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref> the BN bond is relatively strong.

==BBr3==

B3LYP/6-31G(d,p)LANL2DZ

[[File:JOCD_BBR3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000008 0.000450 YES
RMS Force 0.000005 0.000300 YES
Maximum Displacement 0.000036 0.001800 YES
RMS Displacement 0.000023 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_BBR3_FREQ.log| BBr3_frequency.log]]

<pre>
Low frequencies --- -0.0137 -0.0064 -0.0046 2.4315 2.4315 4.8421
Low frequencies --- 155.9631 155.9651 267.7052
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BBR3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

{{DOI|10042/202366}}

==Ionic Liquids==

===[N(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_NCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000076 0.000450 YES
RMS Force 0.000017 0.000300 YES
Maximum Displacement 0.001121 0.001800 YES
RMS Displacement 0.000321 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -9.9670 -0.0011 -0.0007 0.0000 3.4930 8.1265
Low frequencies --- 182.5341 288.5524 288.7594
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===[P(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_PCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000146 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.001509 0.001800 YES
RMS Displacement 0.000498 0.001200 YES
</pre>

Frequency file: [[Media:JOCD_PCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -4.5064 0.0014 0.0029 0.0029 10.2391 13.4026
Low frequencies --- 157.0126 192.4654 192.6170
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_PCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====NBO Charge Analysis====

[[File:JOCD_COMB_CHARGE.png|thumb|center|800px|alt= NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]|NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]]

'''[N(CH3)3]+'''

''Atom'': Charge 
''N'': -0.295,
''C'': -0.483,
''H'': 0.269,

'''[P(CH3)3]+'''

''Atom'': Charge 
''P'': 1.667,
''C'': -1.060,
''H'': 0.298,

The charge analysis shows marked differences in the charge distribution between the two structures. In [P(CH3)3]+
, the positive charge is localised significantly on the phosphorous centre. In comparison the nitrogen centre in [N(CH3)3]+ holds a slight negative charge.

====Molecular Orbital Analysis====

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO10.png
| width1 = 500
| alt1 = Real MO10
| caption1 = Real MO10
| image2 =JOCD_MO10_FO.png
| width2 =500
| alt2 = LCAO MO For MO10
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO13.png
| width1 = 500
| alt1 = Real MO13
| caption1 = Real MO13
| image2 =JOCD_MO13_FO.png
| width2 =500
| alt2 = LCAO MO For MO13
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO19.png
| width1 = 500
| alt1 = Real MO19
| caption1 = Real MO19
| image2 =JOCD_MO19_FO.png
| width2 =500
| alt2 = LCAO MO For MO19
| caption2 = LCAO MO For MO19
}}

Jo416i

2018-05-11T12:01:47Z

Jo416:

==Inorganic Computational Lab==

===BH3===

B3LYP/6-31G(d,p)

[[File:Jocd_bh3_sum.PNG]]

<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 file: [[Media:JOCD_BH3_FREQ.LOG| bh3_frequency.log]]

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0055 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

<jmol><jmolApplet>
<title>optimised BH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====Vibrational spectrum for BH3====
{| class="wikitable"
|+
|-
|wavenumber (cm-1 || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A2''
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|slight
|in-plane-bend
|-
|1213
|14
|E'
|slight
|In-plane-bend
|-
|2582
|0
|A1'
|no
|symmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|}

|[[File:Jocd_bh3_ir.svg|300px]]

Only three peaks are seen in the IR spectrum, despite there being 6 vibrations present. 1 of these vibrations (2582 cm-1) is a symmetric stretch, there is therefore no change in overall dipole moment and thus is not seen in the spectra. There are also two pairs of degenerate vibrations which overlap and therefore you only see 1 peak for each pair. This results in 3 peaks seen in the above spectra.

===BH3 Molecular Orbital Diagram===

[[File:JOCD_BH3_MO.png|frame|none|alt=Alt text|BH33 Molecular Orbital Diagram]]<ref>Hunt, T. (2018) Molecular Orbitals in Inorganic Chemistry. [Lecture] Imperial College London, 2018</ref>

Comparisons of the real molecular orbitals versus the molecular orbitals obtained through LCAO shows the power of molecular orbital theory in predicting real, filled orbitals. However, the accuracy and usefulness of MO theory breaks down for the unoccupied orbitals higher up the diagram. There are significant differences in the contributions of the fragment orbitals predicted vs in the 'real' MOs.

==Association energies: Ammonia-Borane==

===NH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000014 0.001800 YES
RMS Displacement 0.000009 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3_FREQ.LOG| NH3_frequency.log]]

<pre>
Low frequencies --- -0.0128 -0.0010 0.0014 7.1032 8.1046 8.1049
Low frequencies --- 1089.3834 1693.9368 1693.9368
</pre>

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===NH3BH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3BH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000320 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3BH3_FREQ.LOG| NH3BH3_frequency.log]]

<pre>
Low frequencies --- -0.0014 -0.0011 -0.0009 16.8481 17.4133 37.2932
Low frequencies --- 265.8219 632.2116 639.3277
</pre>

<jmol><jmolApplet>
<title>optimised NH3bH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Determining the energy of the dative bond===

E(NH3)=-56.5578 a.u.
E(BH3)=-26.6153 a.u.
E(NH3BH3)=-83.2247 a.u.
ΔE=E(NH3BH3)-[E(BH3)+E(NH3)]
ΔE=-0.0516 a.u.
ΔE=-140 KJ/mol

In comparison with the P-Al dative bond in Me3P→AlMe3 (87.9 KJ/Mol)<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref> the BN bond is relatively strong.

==BBr3==

B3LYP/6-31G(d,p)LANL2DZ

[[File:JOCD_BBR3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000008 0.000450 YES
RMS Force 0.000005 0.000300 YES
Maximum Displacement 0.000036 0.001800 YES
RMS Displacement 0.000023 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_BBR3_FREQ.log| BBr3_frequency.log]]

<pre>
Low frequencies --- -0.0137 -0.0064 -0.0046 2.4315 2.4315 4.8421
Low frequencies --- 155.9631 155.9651 267.7052
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BBR3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

{{DOI|10042/202366}}

==Ionic Liquids==

===[N(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_NCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000076 0.000450 YES
RMS Force 0.000017 0.000300 YES
Maximum Displacement 0.001121 0.001800 YES
RMS Displacement 0.000321 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -9.9670 -0.0011 -0.0007 0.0000 3.4930 8.1265
Low frequencies --- 182.5341 288.5524 288.7594
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===[P(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_PCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000146 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.001509 0.001800 YES
RMS Displacement 0.000498 0.001200 YES
</pre>

Frequency file: [[Media:JOCD_PCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -4.5064 0.0014 0.0029 0.0029 10.2391 13.4026
Low frequencies --- 157.0126 192.4654 192.6170
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_PCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====NBO Charge Analysis====

[[File:JOCD_COMB_CHARGE.png|thumb|center|800px|alt= NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]|NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]]

'''[N(CH3)3]'''

''Atom'': Charge 
''N'': -0.295,
''C'': -0.483,
''H'': 0.269,

'''[P(CH3)3]'''

''Atom'': Charge 
''P'': 1.667,
''C'': -1.060,
''H'': 0.298,

====Molecular Orbital Analysis====

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO10.png
| width1 = 500
| alt1 = Real MO10
| caption1 = Real MO10
| image2 =JOCD_MO10_FO.png
| width2 =500
| alt2 = LCAO MO For MO10
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO13.png
| width1 = 500
| alt1 = Real MO13
| caption1 = Real MO13
| image2 =JOCD_MO13_FO.png
| width2 =500
| alt2 = LCAO MO For MO13
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO19.png
| width1 = 500
| alt1 = Real MO19
| caption1 = Real MO19
| image2 =JOCD_MO19_FO.png
| width2 =500
| alt2 = LCAO MO For MO19
| caption2 = LCAO MO For MO19
}}

Jo416i

2018-05-11T11:55:27Z

Jo416: /* BH3 Molecular Orbital Diagram */

==Inorganic Computational Lab==

===BH3===

B3LYP/6-31G(d,p)

[[File:Jocd_bh3_sum.PNG]]

<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 file: [[Media:JOCD_BH3_FREQ.LOG| bh3_frequency.log]]

<pre>
Low frequencies --- -2.2126 -1.0751 -0.0055 2.2359 10.2633 10.3194
Low frequencies --- 1162.9860 1213.1757 1213.1784
</pre>

<jmol><jmolApplet>
<title>optimised BH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====Vibrational spectrum for BH3====
{| class="wikitable"
|+
|-
|wavenumber (cm-1 || Intensity (arbitrary units) || symmetry || IR active? || type
|-
|1163
|93
|A2''
|yes
|out-of-plane bend
|-
|1213
|14
|E'
|slight
|in-plane-bend
|-
|1213
|14
|E'
|slight
|In-plane-bend
|-
|2582
|0
|A1'
|no
|symmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|-
|2715
|126
|E'
|yes
|asymmetric stretch
|}

|[[File:Jocd_bh3_ir.svg|300px]]

Only three peaks are seen in the IR spectrum, despite there being 6 vibrations present. 1 of these vibrations (2582 cm-1) is a symmetric stretch, there is therefore no change in overall dipole moment and thus is not seen in the spectra. There are also two pairs of degenerate vibrations which overlap and therefore you only see 1 peak for each pair. This results in 3 peaks seen in the above spectra.

===BH3 Molecular Orbital Diagram===

[[File:JOCD_BH3_MO.png|frame|none|alt=Alt text|BH33 Molecular Orbital Diagram]]

Comparisons of the real molecular orbitals versus the molecular orbitals obtained through LCAO shows the power of molecular orbital theory in predicting real, filled orbitals. However, the accuracy and usefulness of MO theory breaks down for the unoccupied orbitals higher up the diagram. There are significant differences in the contributions of the fragment orbitals predicted vs in the 'real' MOs.

==Association energies: Ammonia-Borane==

===NH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000006 0.000450 YES
RMS Force 0.000004 0.000300 YES
Maximum Displacement 0.000014 0.001800 YES
RMS Displacement 0.000009 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3_FREQ.LOG| NH3_frequency.log]]

<pre>
Low frequencies --- -0.0128 -0.0010 0.0014 7.1032 8.1046 8.1049
Low frequencies --- 1089.3834 1693.9368 1693.9368
</pre>

<jmol><jmolApplet>
<title>optimised NH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===NH3BH3===

B3LYP/6-31G(d,p)

[[File:JOCD_NH3BH3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000122 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000582 0.001800 YES
RMS Displacement 0.000320 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NH3BH3_FREQ.LOG| NH3BH3_frequency.log]]

<pre>
Low frequencies --- -0.0014 -0.0011 -0.0009 16.8481 17.4133 37.2932
Low frequencies --- 265.8219 632.2116 639.3277
</pre>

<jmol><jmolApplet>
<title>optimised NH3bH3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NH3BH3_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===Determining the energy of the dative bond===

E(NH3)=-56.5578 a.u.
E(BH3)=-26.6153 a.u.
E(NH3BH3)=-83.2247 a.u.
ΔE=E(NH3BH3)-[E(BH3)+E(NH3)]
ΔE=-0.0516 a.u.
ΔE=-140 KJ/mol

In comparison with the P-Al dative bond in Me3P→AlMe3 (87.9 KJ/Mol)<ref>HAALAND, A. (1989). ChemInform Abstract: Covalent and Dative Bonds to Main Group Metals - A Useful Distinction. ChemInform, 20(43).</ref> the BN bond is relatively strong.

==BBr3==

B3LYP/6-31G(d,p)LANL2DZ

[[File:JOCD_BBR3_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000008 0.000450 YES
RMS Force 0.000005 0.000300 YES
Maximum Displacement 0.000036 0.001800 YES
RMS Displacement 0.000023 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_BBR3_FREQ.log| BBr3_frequency.log]]

<pre>
Low frequencies --- -0.0137 -0.0064 -0.0046 2.4315 2.4315 4.8421
Low frequencies --- 155.9631 155.9651 267.7052
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_BBR3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

{{DOI|10042/202366}}

==Ionic Liquids==

===[N(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_NCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000076 0.000450 YES
RMS Force 0.000017 0.000300 YES
Maximum Displacement 0.001121 0.001800 YES
RMS Displacement 0.000321 0.001200 YES

</pre>

Frequency file: [[Media:JOCD_NCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -9.9670 -0.0011 -0.0007 0.0000 3.4930 8.1265
Low frequencies --- 182.5341 288.5524 288.7594
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_NCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

===[P(CH3)3]+===

B3LYP/6-31G(d,p)

[[File:JOCD_PCH34_SUM.PNG]]

<pre>
Item Value Threshold Converged?
Maximum Force 0.000146 0.000450 YES
RMS Force 0.000032 0.000300 YES
Maximum Displacement 0.001509 0.001800 YES
RMS Displacement 0.000498 0.001200 YES
</pre>

Frequency file: [[Media:JOCD_PCH34_FREQ.LOG| NCH34_frequency.log]]

<pre>
Low frequencies --- -4.5064 0.0014 0.0029 0.0029 10.2391 13.4026
Low frequencies --- 157.0126 192.4654 192.6170
</pre>

<jmol><jmolApplet>
<title>optimised BBr3 molecule</title>
<color>lightgrey</color>
<size>250</size>
<uploadedFileContents>JOCD_PCH34_FREQ.LOG</uploadedFileContents>
</jmolApplet></jmol>

====NBO Charge Analysis====

[[File:JOCD_COMB_CHARGE.png|thumb|center|800px|alt= NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]|NBO charge analysis of [N(CH3)3]+ (left) vs. [P(CH3)3]+]]

'''[N(CH3)3]'''

''Atom'': Charge 
''N'': -0.295,
''C'': -0.483,
''H'': 0.269,

'''[P(CH3)3]'''

''Atom'': Charge 
''P'': 1.667,
''C'': -1.060,
''H'': 0.298,

====Molecular Orbital Analysis====

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO10.png
| width1 = 500
| alt1 = Real MO10
| caption1 = Real MO10
| image2 =JOCD_MO10_FO.png
| width2 =500
| alt2 = LCAO MO For MO10
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO13.png
| width1 = 500
| alt1 = Real MO13
| caption1 = Real MO13
| image2 =JOCD_MO13_FO.png
| width2 =500
| alt2 = LCAO MO For MO13
| caption2 = LCAO
}}

{{multiple image
| direction = horizontal
| align = center
| footer = Comparison of the real molecular orbitals with the LCAO molecular orbitals
| image1 =JOCD_MO19.png
| width1 = 500
| alt1 = Real MO19
| caption1 = Real MO19
| image2 =JOCD_MO19_FO.png
| width2 =500
| alt2 = LCAO MO For MO19
| caption2 = LCAO MO For MO19
}}

Jo416i

2018-05-11T11:49:09Z

Jo416: /* NBO Charge Analysis */

Jo416i

2018-05-11T11:47:31Z

Jo416: /* NBO Charge Analysis */

Jo416i

2018-05-11T11:47:03Z

Jo416: /* NBO Charge Analysis */

File:JOCD COMB CHARGE.png

2018-05-11T11:31:01Z

Jo416:

Jo416i

2018-05-11T10:41:42Z

Jo416: /* NBO Charge Analysis */

Jo416i

2018-05-11T10:32:33Z

Jo416:

Jo416i

2018-05-11T10:31:02Z

Jo416:

Jo416i

2018-05-11T10:29:00Z

Jo416:

Jo416i

2018-05-11T10:26:09Z

Jo416:

Jo416i

2018-05-11T10:23:14Z

Jo416:

Jo416i

2018-05-11T10:20:04Z

Jo416:

Jo416i

2018-05-11T10:17:18Z

Jo416:

Jo416i

2018-05-11T09:52:08Z

Jo416:

File:JOCD MO19 FO.png

2018-05-11T09:47:51Z

Jo416:

File:JOCD MO13 FO.png

2018-05-11T09:47:21Z

Jo416:

File:JOCD MO10 FO.png

2018-05-11T09:46:57Z

Jo416:

Jo416i

2018-05-11T09:46:11Z

Jo416:

Jo416i

2018-05-11T09:41:25Z

Jo416:

Jo416i

2018-05-10T15:19:42Z

Jo416:

File:JOCD MO19.png

2018-05-10T15:17:40Z

Jo416:

File:JOCD MO13.png

2018-05-10T15:17:04Z

Jo416:

File:JOCD MO10.png

2018-05-10T15:16:45Z

Jo416:

Jo416i

2018-05-10T14:04:39Z

Jo416: /* NBO Charge Analysis */

Jo416i

2018-05-10T14:04:15Z

Jo416:

Jo416i

2018-05-10T14:02:44Z

Jo416: /* NBO Charge Analysis */

Jo416i

2018-05-10T14:01:18Z

Jo416: /* NBO Charge Analysis */

Jo416i

2018-05-10T14:00:10Z

Jo416: /* NBO Charge Analysis */

Jo416i

2018-05-10T13:55:19Z

Jo416:

Jo416i

2018-05-10T13:53:42Z

Jo416: /* NBO Charge Analysis */

Jo416i

2018-05-10T13:52:39Z

Jo416: /* NBO Charge Analysis */

Jo416i

2018-05-10T13:51:29Z

Jo416: /* NBO Charge Analysis */

Jo416i

2018-05-10T13:51:07Z

Jo416:

Jo416i

2018-05-10T13:41:49Z

Jo416: