2019-05-24T13:45:50Z

Vm3717: /* Simplified MO Representation of N(CH3)4+ */

== BH3 ==

B3LYP/6-31G(d,p)

<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:VLAD_BH3_FREQ.log| VLAD_BH3_FREQ.log]]

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

[[File:Gaussian calcilation summary BH3.png]]

[[File:Gaussian IRFrequencies BH3.png]]

[[File:Gaussian IRspectrum BH3.png]]

The spectrum shows only 3 peaks, because two pairs of vibrations are degenerate and one vibration is not IR active since there is no net change in dipole moment.

<jmol><jmolApplet>
<title>Optimised BH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>VLAD_BH3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

[[File:Labelled MO DIA.png]]

REFERENCE!

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

At lower energies the real MOs look exactly like predicted by the LCAO MOs; however, at higher energies, the superposition of out of phase LCAOs might be quite complicated, but when it is done they still look similar.

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

This shows that the qualitative MO theory is useful and accurate.

==NH3BH3==

==NH3 Energy Calculation==

B3LYP/6-31G(d,p)

<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>

<pre>

Low frequencies --- -0.0128 -0.0017 0.0013 7.1034 8.1048 8.1051
Low frequencies --- 1089.3834 1693.9368 1693.9368

</pre>

Frequency File: [[Media:NH3 ENERGY CALC.LOG| NH3 ENERGY CALC.LOG]]

[[File:NH3 SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised NH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>NH3 ENERGY CALC.LOG</uploadedFileContents>
</jmolApplet></jmol>

==BH3NH3 Energy Calculation==

B3LYP/6-31G(d,p)

<pre>
Item Value Threshold Converged?
Maximum Force 0.000123 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000585 0.001800 YES
RMS Displacement 0.000320 0.001200 YES
</pre>

<pre>
Low frequencies --- -0.0006 0.0011 0.0012 16.8436 17.4462 37.3291
Low frequencies --- 265.8243 632.2043 639.3227
</pre>

Frequency File: [[Media:NH3 BH3 CALC.LOG|NH3 BH3 CALC.LOG]]

[[File:BH3NH3 ENERGY Summary.png]]

<jmol><jmolApplet>
<title>Optimised BH3NH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>NH3 BH3 CALC.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association Energy Calculation==

E(NH3)= -56.55776873 a.u.
E(BH3)= -26.61532363 a.u.
E(NH3BH3)= -83.22468893 a.u.

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)] = -0.05159657 a.u. = -135kJ/mol

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

B-H average bond energy literature value is 389kJ/mol (Reference Data Series," National Bureau of Standards, No. 31, Washington, DC, 1970; S.W. Benson, J. Chem. Educ., 42, 502 (1965).)

N-H average bond energy value is 391 kJ/mol (Referenced from Chemistry by Zumdahl (5th ed.) Table 8.4 on page 373)

Compared to the N-H and B-H bond energies the dative B-N bond appears to be relatively weak.

==NI3 Molecule Optimisation==

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

<pre>
Item Value Threshold Converged?
Maximum Force 0.000088 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000858 0.001800 YES
RMS Displacement 0.000481 0.001200 YES
</pre>

<pre>
Low frequencies --- -12.3847 -12.3783 -5.6131 -0.0040 0.0194 0.0711
Low frequencies --- 100.9307 100.9314 147.2333
</pre>

Frequency File: [[Media:VM NI3 FREQUENCY.LOG|VM NI3 FREQUENCY.LOG]]

[[File:VM NI3 FREQUENCY SUM.png]]

<jmol><jmolApplet>
<title>Optimised NI3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>VM NI3 FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

N-I bond distance: 2.18424 Å

==Day 2 Project: Ionic Liquids==

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

B3LYP/3-21G level

<pre>

Item Value Threshold Converged?
Maximum Force 0.000104 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.001280 0.001800 YES
RMS Displacement 0.000471 0.001200 YES
</pre>

<pre>
Low frequencies --- -5.1443 0.0001 0.0002 0.0008 8.6939 10.0026
Low frequencies --- 185.0713 289.7367 290.3827
</pre>

Frequency File: [[Media:N(CH3)4+ FREQUENCY.LOG|N(CH3)4+ FREQUENCY.LOG]]

[[File:N(CH3)4+ SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised N(CH3)4+</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>N(CH3)4+ FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''P(CH3)4+'''

B3LYP/3-21G level

<pre>

Item Value Threshold Converged?
Maximum Force 0.000035 0.000450 YES
RMS Force 0.000016 0.000300 YES
Maximum Displacement 0.001592 0.001800 YES
RMS Displacement 0.000629 0.001200 YES
</pre>

<pre>
Low frequencies --- -8.7146 -0.0025 -0.0020 -0.0001 5.1179 7.2785
Low frequencies --- 157.0823 192.6438 193.0924
</pre>

Frequency File: [[Media:P(CH3)4+ FREQUENCY.LOG|P(CH3)4+ FREQUENCY.LOG]]

[[File:P(CH3)4+ FREQUENCY SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised P(CH3)4+</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>P(CH3)4+ FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Charge Distributions:
'''

== N(CH3)4+: ==

[[File:Charge Distribution N(CH3)4+.png]]

N: -0.26
C: -0.48
H: +0.27

== P(CH3)4+: ==

[[File:P(CH3)4 CHARGEDISTRIBUTION.png]]

P: +1.7
C:-1.1
H:+0.30

The two structures are symetrically similar, thus we can compare them based on the charge distribution differences. For example, we can see that the phosphorus atom is more electropositive than the nitrogen atom, thus it carries a higher electrical charge. Due to the same reason (phosphorus is more electropositive than nitrogen), the carbon in the phosphorus molecule carries a higher negative charge. Even though the nitrogen is a more electronegative atom than carbon, it carries a higher charge, because initially an electron was removed from it in order for this ion to form.

== Questions ==

''What does the "formal" positive charge on the N represent in the traditional picture?''

In the traditional picture formal charge is the charge on the N atom assuming that all atoms share electron density equally, thus disregarding the effects of electronegativity. In reality, the electronegativity is important for the real picture consideration and the charge on the Nitrogen atom is not +1.

''On what atoms is the positive charge actually located for this cation?''

As a result of the molecule optimisation, we can see that the positive charge is located on the hydrogen atoms.

==Simplified MO Representation of N(CH3)4+==

[[File:Mo 10 DIA.png]]

[[File:MO 10.png]]

File:MO 10.png

2019-05-24T13:45:27Z

Vm3717: Vm3717 uploaded a new version of File:MO 10.png

[[File:MO_10.png]]

Vm371798

2019-05-24T13:44:53Z

Vm3717:

== BH3 ==

B3LYP/6-31G(d,p)

<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:VLAD_BH3_FREQ.log| VLAD_BH3_FREQ.log]]

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

[[File:Gaussian calcilation summary BH3.png]]

[[File:Gaussian IRFrequencies BH3.png]]

[[File:Gaussian IRspectrum BH3.png]]

The spectrum shows only 3 peaks, because two pairs of vibrations are degenerate and one vibration is not IR active since there is no net change in dipole moment.

<jmol><jmolApplet>
<title>Optimised BH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>VLAD_BH3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

[[File:Labelled MO DIA.png]]

REFERENCE!

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

At lower energies the real MOs look exactly like predicted by the LCAO MOs; however, at higher energies, the superposition of out of phase LCAOs might be quite complicated, but when it is done they still look similar.

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

This shows that the qualitative MO theory is useful and accurate.

==NH3BH3==

==NH3 Energy Calculation==

B3LYP/6-31G(d,p)

<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>

<pre>

Low frequencies --- -0.0128 -0.0017 0.0013 7.1034 8.1048 8.1051
Low frequencies --- 1089.3834 1693.9368 1693.9368

</pre>

Frequency File: [[Media:NH3 ENERGY CALC.LOG| NH3 ENERGY CALC.LOG]]

[[File:NH3 SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised NH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>NH3 ENERGY CALC.LOG</uploadedFileContents>
</jmolApplet></jmol>

==BH3NH3 Energy Calculation==

B3LYP/6-31G(d,p)

<pre>
Item Value Threshold Converged?
Maximum Force 0.000123 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000585 0.001800 YES
RMS Displacement 0.000320 0.001200 YES
</pre>

<pre>
Low frequencies --- -0.0006 0.0011 0.0012 16.8436 17.4462 37.3291
Low frequencies --- 265.8243 632.2043 639.3227
</pre>

Frequency File: [[Media:NH3 BH3 CALC.LOG|NH3 BH3 CALC.LOG]]

[[File:BH3NH3 ENERGY Summary.png]]

<jmol><jmolApplet>
<title>Optimised BH3NH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>NH3 BH3 CALC.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association Energy Calculation==

E(NH3)= -56.55776873 a.u.
E(BH3)= -26.61532363 a.u.
E(NH3BH3)= -83.22468893 a.u.

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)] = -0.05159657 a.u. = -135kJ/mol

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

B-H average bond energy literature value is 389kJ/mol (Reference Data Series," National Bureau of Standards, No. 31, Washington, DC, 1970; S.W. Benson, J. Chem. Educ., 42, 502 (1965).)

N-H average bond energy value is 391 kJ/mol (Referenced from Chemistry by Zumdahl (5th ed.) Table 8.4 on page 373)

Compared to the N-H and B-H bond energies the dative B-N bond appears to be relatively weak.

==NI3 Molecule Optimisation==

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

<pre>
Item Value Threshold Converged?
Maximum Force 0.000088 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000858 0.001800 YES
RMS Displacement 0.000481 0.001200 YES
</pre>

<pre>
Low frequencies --- -12.3847 -12.3783 -5.6131 -0.0040 0.0194 0.0711
Low frequencies --- 100.9307 100.9314 147.2333
</pre>

Frequency File: [[Media:VM NI3 FREQUENCY.LOG|VM NI3 FREQUENCY.LOG]]

[[File:VM NI3 FREQUENCY SUM.png]]

<jmol><jmolApplet>
<title>Optimised NI3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>VM NI3 FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

N-I bond distance: 2.18424 Å

==Day 2 Project: Ionic Liquids==

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

B3LYP/3-21G level

<pre>

Item Value Threshold Converged?
Maximum Force 0.000104 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.001280 0.001800 YES
RMS Displacement 0.000471 0.001200 YES
</pre>

<pre>
Low frequencies --- -5.1443 0.0001 0.0002 0.0008 8.6939 10.0026
Low frequencies --- 185.0713 289.7367 290.3827
</pre>

Frequency File: [[Media:N(CH3)4+ FREQUENCY.LOG|N(CH3)4+ FREQUENCY.LOG]]

[[File:N(CH3)4+ SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised N(CH3)4+</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>N(CH3)4+ FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''P(CH3)4+'''

B3LYP/3-21G level

<pre>

Item Value Threshold Converged?
Maximum Force 0.000035 0.000450 YES
RMS Force 0.000016 0.000300 YES
Maximum Displacement 0.001592 0.001800 YES
RMS Displacement 0.000629 0.001200 YES
</pre>

<pre>
Low frequencies --- -8.7146 -0.0025 -0.0020 -0.0001 5.1179 7.2785
Low frequencies --- 157.0823 192.6438 193.0924
</pre>

Frequency File: [[Media:P(CH3)4+ FREQUENCY.LOG|P(CH3)4+ FREQUENCY.LOG]]

[[File:P(CH3)4+ FREQUENCY SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised P(CH3)4+</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>P(CH3)4+ FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Charge Distributions:
'''

== N(CH3)4+: ==

[[File:Charge Distribution N(CH3)4+.png]]

N: -0.26
C: -0.48
H: +0.27

== P(CH3)4+: ==

[[File:P(CH3)4 CHARGEDISTRIBUTION.png]]

P: +1.7
C:-1.1
H:+0.30

The two structures are symetrically similar, thus we can compare them based on the charge distribution differences. For example, we can see that the phosphorus atom is more electropositive than the nitrogen atom, thus it carries a higher electrical charge. Due to the same reason (phosphorus is more electropositive than nitrogen), the carbon in the phosphorus molecule carries a higher negative charge. Even though the nitrogen is a more electronegative atom than carbon, it carries a higher charge, because initially an electron was removed from it in order for this ion to form.

== Questions ==

''What does the "formal" positive charge on the N represent in the traditional picture?''

In the traditional picture formal charge is the charge on the N atom assuming that all atoms share electron density equally, thus disregarding the effects of electronegativity. In reality, the electronegativity is important for the real picture consideration and the charge on the Nitrogen atom is not +1.

''On what atoms is the positive charge actually located for this cation?''

As a result of the molecule optimisation, we can see that the positive charge is located on the hydrogen atoms.

==Simplified MO Representation of N(CH3)4+==

[[File:Mo 10 DIA.png]]

File:Mo 10 DIA.png

2019-05-24T13:42:29Z

Vm3717:

Vm371798

2019-05-24T12:50:12Z

Vm3717: /* BH3 */

== BH3 ==

B3LYP/6-31G(d,p)

<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:VLAD_BH3_FREQ.log| VLAD_BH3_FREQ.log]]

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

[[File:Gaussian calcilation summary BH3.png]]

[[File:Gaussian IRFrequencies BH3.png]]

[[File:Gaussian IRspectrum BH3.png]]

The spectrum shows only 3 peaks, because two pairs of vibrations are degenerate and one vibration is not IR active since there is no net change in dipole moment.

<jmol><jmolApplet>
<title>Optimised BH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>VLAD_BH3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

[[File:Labelled MO DIA.png]]

REFERENCE!

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

At lower energies the real MOs look exactly like predicted by the LCAO MOs; however, at higher energies, the superposition of out of phase LCAOs might be quite complicated, but when it is done they still look similar.

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

This shows that the qualitative MO theory is useful and accurate.

==NH3BH3==

==NH3 Energy Calculation==

B3LYP/6-31G(d,p)

<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>

<pre>

Low frequencies --- -0.0128 -0.0017 0.0013 7.1034 8.1048 8.1051
Low frequencies --- 1089.3834 1693.9368 1693.9368

</pre>

Frequency File: [[Media:NH3 ENERGY CALC.LOG| NH3 ENERGY CALC.LOG]]

[[File:NH3 SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised NH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>NH3 ENERGY CALC.LOG</uploadedFileContents>
</jmolApplet></jmol>

==BH3NH3 Energy Calculation==

B3LYP/6-31G(d,p)

<pre>
Item Value Threshold Converged?
Maximum Force 0.000123 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000585 0.001800 YES
RMS Displacement 0.000320 0.001200 YES
</pre>

<pre>
Low frequencies --- -0.0006 0.0011 0.0012 16.8436 17.4462 37.3291
Low frequencies --- 265.8243 632.2043 639.3227
</pre>

Frequency File: [[Media:NH3 BH3 CALC.LOG|NH3 BH3 CALC.LOG]]

[[File:BH3NH3 ENERGY Summary.png]]

<jmol><jmolApplet>
<title>Optimised BH3NH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>NH3 BH3 CALC.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association Energy Calculation==

E(NH3)= -56.55776873 a.u.
E(BH3)= -26.61532363 a.u.
E(NH3BH3)= -83.22468893 a.u.

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)] = -0.05159657 a.u. = -135kJ/mol

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

B-H average bond energy literature value is 389kJ/mol (Reference Data Series," National Bureau of Standards, No. 31, Washington, DC, 1970; S.W. Benson, J. Chem. Educ., 42, 502 (1965).)

N-H average bond energy value is 391 kJ/mol (Referenced from Chemistry by Zumdahl (5th ed.) Table 8.4 on page 373)

Compared to the N-H and B-H bond energies the dative B-N bond appears to be relatively weak.

==NI3 Molecule Optimisation==

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

<pre>
Item Value Threshold Converged?
Maximum Force 0.000088 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000858 0.001800 YES
RMS Displacement 0.000481 0.001200 YES
</pre>

<pre>
Low frequencies --- -12.3847 -12.3783 -5.6131 -0.0040 0.0194 0.0711
Low frequencies --- 100.9307 100.9314 147.2333
</pre>

Frequency File: [[Media:VM NI3 FREQUENCY.LOG|VM NI3 FREQUENCY.LOG]]

[[File:VM NI3 FREQUENCY SUM.png]]

<jmol><jmolApplet>
<title>Optimised NI3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>VM NI3 FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

N-I bond distance: 2.18424 Å

==Day 2 Project: Ionic Liquids==

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

B3LYP/3-21G level

<pre>

Item Value Threshold Converged?
Maximum Force 0.000104 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.001280 0.001800 YES
RMS Displacement 0.000471 0.001200 YES
</pre>

<pre>
Low frequencies --- -5.1443 0.0001 0.0002 0.0008 8.6939 10.0026
Low frequencies --- 185.0713 289.7367 290.3827
</pre>

Frequency File: [[Media:N(CH3)4+ FREQUENCY.LOG|N(CH3)4+ FREQUENCY.LOG]]

[[File:N(CH3)4+ SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised N(CH3)4+</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>N(CH3)4+ FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''P(CH3)4+'''

B3LYP/3-21G level

<pre>

Item Value Threshold Converged?
Maximum Force 0.000035 0.000450 YES
RMS Force 0.000016 0.000300 YES
Maximum Displacement 0.001592 0.001800 YES
RMS Displacement 0.000629 0.001200 YES
</pre>

<pre>
Low frequencies --- -8.7146 -0.0025 -0.0020 -0.0001 5.1179 7.2785
Low frequencies --- 157.0823 192.6438 193.0924
</pre>

Frequency File: [[Media:P(CH3)4+ FREQUENCY.LOG|P(CH3)4+ FREQUENCY.LOG]]

[[File:P(CH3)4+ FREQUENCY SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised P(CH3)4+</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>P(CH3)4+ FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''Charge Distributions:
'''

== N(CH3)4+: ==

[[File:Charge Distribution N(CH3)4+.png]]

N: -0.26
C: -0.48
H: +0.27

== P(CH3)4+: ==

[[File:P(CH3)4 CHARGEDISTRIBUTION.png]]

P: +1.7
C:-1.1
H:+0.30

The two structures are symetrically similar, thus we can compare them based on the charge distribution differences. For example, we can see that the phosphorus atom is more electropositive than the nitrogen atom, thus it carries a higher electrical charge. Due to the same reason (phosphorus is more electropositive than nitrogen), the carbon in the phosphorus molecule carries a higher negative charge. Even though the nitrogen is a more electronegative atom than carbon, it carries a higher charge, because initially an electron was removed from it in order for this ion to form.

== Questions ==

''What does the "formal" positive charge on the N represent in the traditional picture?''

In the traditional picture formal charge is the charge on the N atom assuming that all atoms share electron density equally, thus disregarding the effects of electronegativity. In reality, the electronegativity is important for the real picture consideration and the charge on the Nitrogen atom is not +1.

''On what atoms is the positive charge actually located for this cation?''

As a result of the molecule optimisation, we can see that the positive charge is located on the hydrogen atoms.

File:Labelled MO DIA.png

2019-05-24T12:48:44Z

Vm3717:

2019-05-24T11:58:16Z

Vm3717:

File:Charge Distribution N(CH3)4+.png

2019-05-24T11:57:03Z

Vm3717:

Vm371798

2019-05-24T11:45:03Z

Vm3717: /* Day 2 Project: Ionic Liquids */

== BH3 ==

B3LYP/6-31G(d,p)

<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:VLAD_BH3_FREQ.log| VLAD_BH3_FREQ.log]]

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

[[File:Gaussian calcilation summary BH3.png]]

[[File:Gaussian IRFrequencies BH3.png]]

[[File:Gaussian IRspectrum BH3.png]]

The spectrum shows only 3 peaks, because two pairs of vibrations are degenerate and one vibration is not IR active since there is no net change in dipole moment.

<jmol><jmolApplet>
<title>Optimised BH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>VLAD_BH3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

[[File:BH3 MOS DIA.png]]

REFERENCE!

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

At lower energies the real MOs look exactly like predicted by the LCAO MOs; however, at higher energies, the superposition of out of phase LCAOs might be quite complicated, but when it is done they still look similar.

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

This shows that the qualitative MO theory is useful and accurate.

==NH3BH3==

==NH3 Energy Calculation==

B3LYP/6-31G(d,p)

<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>

<pre>

Low frequencies --- -0.0128 -0.0017 0.0013 7.1034 8.1048 8.1051
Low frequencies --- 1089.3834 1693.9368 1693.9368

</pre>

Frequency File: [[Media:NH3 ENERGY CALC.LOG| NH3 ENERGY CALC.LOG]]

[[File:NH3 SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised NH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>NH3 ENERGY CALC.LOG</uploadedFileContents>
</jmolApplet></jmol>

==BH3NH3 Energy Calculation==

B3LYP/6-31G(d,p)

<pre>
Item Value Threshold Converged?
Maximum Force 0.000123 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000585 0.001800 YES
RMS Displacement 0.000320 0.001200 YES
</pre>

<pre>
Low frequencies --- -0.0006 0.0011 0.0012 16.8436 17.4462 37.3291
Low frequencies --- 265.8243 632.2043 639.3227
</pre>

Frequency File: [[Media:NH3 BH3 CALC.LOG|NH3 BH3 CALC.LOG]]

[[File:BH3NH3 ENERGY Summary.png]]

<jmol><jmolApplet>
<title>Optimised BH3NH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>NH3 BH3 CALC.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association Energy Calculation==

E(NH3)= -56.55776873 a.u.
E(BH3)= -26.61532363 a.u.
E(NH3BH3)= -83.22468893 a.u.

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)] = -0.05159657 a.u. = -135kJ/mol

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

B-H average bond energy literature value is 389kJ/mol (Reference Data Series," National Bureau of Standards, No. 31, Washington, DC, 1970; S.W. Benson, J. Chem. Educ., 42, 502 (1965).)

N-H average bond energy value is 391 kJ/mol (Referenced from Chemistry by Zumdahl (5th ed.) Table 8.4 on page 373)

Compared to the N-H and B-H bond energies the dative B-N bond appears to be relatively weak.

==NI3 Molecule Optimisation==

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

<pre>
Item Value Threshold Converged?
Maximum Force 0.000088 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000858 0.001800 YES
RMS Displacement 0.000481 0.001200 YES
</pre>

<pre>
Low frequencies --- -12.3847 -12.3783 -5.6131 -0.0040 0.0194 0.0711
Low frequencies --- 100.9307 100.9314 147.2333
</pre>

Frequency File: [[Media:VM NI3 FREQUENCY.LOG|VM NI3 FREQUENCY.LOG]]

[[File:VM NI3 FREQUENCY SUM.png]]

<jmol><jmolApplet>
<title>Optimised NI3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>VM NI3 FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

N-I bond distance: 2.18424 Å

==Day 2 Project: Ionic Liquids==

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

B3LYP/3-21G level

<pre>

Item Value Threshold Converged?
Maximum Force 0.000104 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.001280 0.001800 YES
RMS Displacement 0.000471 0.001200 YES
</pre>

<pre>
Low frequencies --- -5.1443 0.0001 0.0002 0.0008 8.6939 10.0026
Low frequencies --- 185.0713 289.7367 290.3827
</pre>

Frequency File: [[Media:N(CH3)4+ FREQUENCY.LOG|N(CH3)4+ FREQUENCY.LOG]]

[[File:N(CH3)4+ SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised N(CH3)4+</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>N(CH3)4+ FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''P(CH3)4+'''

B3LYP/3-21G level

<pre>

Item Value Threshold Converged?
Maximum Force 0.000035 0.000450 YES
RMS Force 0.000016 0.000300 YES
Maximum Displacement 0.001592 0.001800 YES
RMS Displacement 0.000629 0.001200 YES
</pre>

<pre>
Low frequencies --- -8.7146 -0.0025 -0.0020 -0.0001 5.1179 7.2785
Low frequencies --- 157.0823 192.6438 193.0924
</pre>

Frequency File: [[Media:P(CH3)4+ FREQUENCY.LOG|P(CH3)4+ FREQUENCY.LOG]]

[[File:P(CH3)4+ FREQUENCY SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised P(CH3)4+</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>P(CH3)4+ FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

Vm371798

2019-05-24T11:44:50Z

Vm3717: /* Day 2 Project: Ionic Liquids */

== BH3 ==

B3LYP/6-31G(d,p)

<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:VLAD_BH3_FREQ.log| VLAD_BH3_FREQ.log]]

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

[[File:Gaussian calcilation summary BH3.png]]

[[File:Gaussian IRFrequencies BH3.png]]

[[File:Gaussian IRspectrum BH3.png]]

The spectrum shows only 3 peaks, because two pairs of vibrations are degenerate and one vibration is not IR active since there is no net change in dipole moment.

<jmol><jmolApplet>
<title>Optimised BH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>VLAD_BH3_FREQ.log</uploadedFileContents>
</jmolApplet></jmol>

[[File:BH3 MOS DIA.png]]

REFERENCE!

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

At lower energies the real MOs look exactly like predicted by the LCAO MOs; however, at higher energies, the superposition of out of phase LCAOs might be quite complicated, but when it is done they still look similar.

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

This shows that the qualitative MO theory is useful and accurate.

==NH3BH3==

==NH3 Energy Calculation==

B3LYP/6-31G(d,p)

<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>

<pre>

Low frequencies --- -0.0128 -0.0017 0.0013 7.1034 8.1048 8.1051
Low frequencies --- 1089.3834 1693.9368 1693.9368

</pre>

Frequency File: [[Media:NH3 ENERGY CALC.LOG| NH3 ENERGY CALC.LOG]]

[[File:NH3 SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised NH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>NH3 ENERGY CALC.LOG</uploadedFileContents>
</jmolApplet></jmol>

==BH3NH3 Energy Calculation==

B3LYP/6-31G(d,p)

<pre>
Item Value Threshold Converged?
Maximum Force 0.000123 0.000450 YES
RMS Force 0.000058 0.000300 YES
Maximum Displacement 0.000585 0.001800 YES
RMS Displacement 0.000320 0.001200 YES
</pre>

<pre>
Low frequencies --- -0.0006 0.0011 0.0012 16.8436 17.4462 37.3291
Low frequencies --- 265.8243 632.2043 639.3227
</pre>

Frequency File: [[Media:NH3 BH3 CALC.LOG|NH3 BH3 CALC.LOG]]

[[File:BH3NH3 ENERGY Summary.png]]

<jmol><jmolApplet>
<title>Optimised BH3NH3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>NH3 BH3 CALC.LOG</uploadedFileContents>
</jmolApplet></jmol>

==Association Energy Calculation==

E(NH3)= -56.55776873 a.u.
E(BH3)= -26.61532363 a.u.
E(NH3BH3)= -83.22468893 a.u.

ΔE=E(NH3BH3)-[E(NH3)+E(BH3)] = -0.05159657 a.u. = -135kJ/mol

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

B-H average bond energy literature value is 389kJ/mol (Reference Data Series," National Bureau of Standards, No. 31, Washington, DC, 1970; S.W. Benson, J. Chem. Educ., 42, 502 (1965).)

N-H average bond energy value is 391 kJ/mol (Referenced from Chemistry by Zumdahl (5th ed.) Table 8.4 on page 373)

Compared to the N-H and B-H bond energies the dative B-N bond appears to be relatively weak.

==NI3 Molecule Optimisation==

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

<pre>
Item Value Threshold Converged?
Maximum Force 0.000088 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.000858 0.001800 YES
RMS Displacement 0.000481 0.001200 YES
</pre>

<pre>
Low frequencies --- -12.3847 -12.3783 -5.6131 -0.0040 0.0194 0.0711
Low frequencies --- 100.9307 100.9314 147.2333
</pre>

Frequency File: [[Media:VM NI3 FREQUENCY.LOG|VM NI3 FREQUENCY.LOG]]

[[File:VM NI3 FREQUENCY SUM.png]]

<jmol><jmolApplet>
<title>Optimised NI3 Molecule</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>VM NI3 FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

N-I bond distance: 2.18424 Å

==Day 2 Project: Ionic Liquids==

'''[N(CH3)4]+
'''
B3LYP/3-21G level

<pre>

Item Value Threshold Converged?
Maximum Force 0.000104 0.000450 YES
RMS Force 0.000044 0.000300 YES
Maximum Displacement 0.001280 0.001800 YES
RMS Displacement 0.000471 0.001200 YES
</pre>

<pre>
Low frequencies --- -5.1443 0.0001 0.0002 0.0008 8.6939 10.0026
Low frequencies --- 185.0713 289.7367 290.3827
</pre>

Frequency File: [[Media:N(CH3)4+ FREQUENCY.LOG|N(CH3)4+ FREQUENCY.LOG]]

[[File:N(CH3)4+ SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised N(CH3)4+</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>N(CH3)4+ FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

'''P(CH3)4+'''

B3LYP/3-21G level

<pre>

Item Value Threshold Converged?
Maximum Force 0.000035 0.000450 YES
RMS Force 0.000016 0.000300 YES
Maximum Displacement 0.001592 0.001800 YES
RMS Displacement 0.000629 0.001200 YES
</pre>

<pre>
Low frequencies --- -8.7146 -0.0025 -0.0020 -0.0001 5.1179 7.2785
Low frequencies --- 157.0823 192.6438 193.0924
</pre>

Frequency File: [[Media:P(CH3)4+ FREQUENCY.LOG|P(CH3)4+ FREQUENCY.LOG]]

[[File:P(CH3)4+ FREQUENCY SUMMARY.png]]

<jmol><jmolApplet>
<title>Optimised P(CH3)4+</title>
<color>lightgrey</color>
<size>200</size>
<uploadedFileContents>P(CH3)4+ FREQUENCY.LOG</uploadedFileContents>
</jmolApplet></jmol>

Vm371798

2019-05-24T11:44:11Z

2019-05-23T16:42:18Z

Vm3717:

Vm371798

2019-05-23T16:41:08Z

Vm3717: