Robertisla

Lab1 Marking

You did a great job especially with the formatting. However, you have tabulated wrong charges for N and F. If you have any queries, please contact Prof. Hunt.

BH₃ Molecule

Calculation data

name of submitted log file	IR_BH3_OPTF_POP.LOG
molecule	NH3
method	RB3LYP
basis set	6-31G(d,p)
final energy	-26.615112
RMS gradient	0.003053
point group	D3h

Item Table

        Item               Value     Threshold  Converged?
 Maximum Force            0.000004     0.000015     YES
 RMS     Force            0.000003     0.000010     YES
 Maximum Displacement     0.000017     0.000060     YES
 RMS     Displacement     0.000011     0.000040     YES

Low frequencies data

Low frequencies	-11.6940	-11.6861	-6.5543	0.0007	0.0280	0.4289
Low frequencies	1162.9745	1213.1390	1213.1392

Optimised molecule image

Jmol rotateable molecule

logfile: Media:IR BH3 OPTF POP.LOG

optimised BH molecule

Important geometric parameters

Optimised bond distance and angle for BH₃
r(B-H)=1.19Â
θ(H-B-H)=120°

Vibrational data

Mode	1	2	3	4	5	6
Wavenumber (cm-1)	1163	1213	1213	2583	2716	2716
Symmetry	A2"	E'	E'	A1'	E'	E'
Intensity (arbitrary)	93	14	14	0	126	126

BH₃NH₃ Molecule

Calculation data

name of submitted log file	IR_NH3BH3_OPT.LOG
molecule	NH3BH3
method	RB3LYP
basis set	6-31G(d,p)
final energy	-83.22489
RMS gradient	0.000001
point group	C1

Item Table

           Item               Value     Threshold  Converged?
 Maximum Force            0.000001     0.000015     YES
 RMS     Force            0.000001     0.000010     YES
 Maximum Displacement     0.000043     0.000060     YES
 RMS     Displacement     0.000019     0.000040     YES

Low frequencies data

Low frequencies	-5.0461	-2.8839	-0.0019	-0.0009	-0.0005	0.6099
Low frequencies	263.3824	632.9842	638.4292

Optimised molecule image

Jmol rotateable molecule

logfile: Media:IR_NH3BH3_OPT.LOG

optimised NHBH molecule

Important geometric parameters

Optimised bond distance and angle for NH₃BH₃
r(B-H)=1.210Â
r(N-H)=1.018Â
r(N-B)=1.668Â
θ(H-B-H)=114°
θ(H-N-H)=108°
θ(H-N-B)=111°
θ(H-B-N)=105°

Vibrational data

Mode	1	2	3	4	5	6	7	8	9	10	11	12	13	14	15	16	17	18
Wavenumber (cm-1)	263	633	638	638	1069	1069	1196	1204	1204	1329	1676	1676	2472	2532	2532	3464	3581	3581
Symmetry	A	A	A	A	A	A	A	A	A	A	A	A	A	A	A	A	A	A
Intensity (arbitrary)	0	14	4	4	41	41	109	3	3	114	28	28	67	231	231	3	28	28

Total energies

E (NH₃) = -56.557769
E (BH₃) = -26.615112
E (BH₃NH₃) = -83.22489

Association Energy

ΔE= E(NH3BH3)-[E(NH3)+E(BH3)]
ΔE= -0.051989 Au
ΔE= -136.49712 Kj/mol (5 d.p.)

Me₃NH-CL Molecule

Calculation data

name of submitted log file	IR_ME3NH-CL_OPT2.LOG
molecule	Me3NH-Cl
method	RB3LYP
basis set	6-31G(d,p)
final energy	-26.615112
RMS gradient	0.003053
point group	D3H

Item Table

         Item               Value     Threshold  Converged?
 Maximum Force            0.000019     0.000450     YES
 RMS     Force            0.000005     0.000300     YES
 Maximum Displacement     0.001834     0.001800     NO 
 RMS     Displacement     0.000343     0.001200     YES

Low frequencies data

Low frequencies	-13.7046	-2.3785	-0.0021	-0.0019	0.0012	1.7651
Low frequencies	55.6029	56.2004	189.7955

Optimised molecule image

Jmol rotateable molecule

logfile: Media:IR_ME3NH-CL_OPT2.LOG

optimised MeNH-Cl molecule

Important geometric parameters

r(N-H)= 1.16395
r(H-Cl)= 1.73817
r(N-Cl)= 2.90211

Rigid Scan for Me₃NH-Cl

PES Raw data plot

PES raw data table

Scan Coordinate Â	Total Energy (Hartrees)	Relative Total Energy kJ mol -1
0.8000000000	-632.0662501520	229.8654262
0.9000000000	-632.1224191760	82.39365367
1.0000000000	-632.1460481500	20.35578243
1.1000000000	-632.1535070430	0.772458857
1.2000000000	-632.1538012570	0
1.3000000000	-632.1515762760	5.841687616
1.4000000000	-632.1490196910	12.55400153
1.5000000000	-632.1470179040	17.8096933
1.6000000000	-632.1457415820	21.16067671
1.7000000000	-632.1447845590	23.6733406
1.8000000000	-632.1429342760	28.53125862
1.9000000000	-632.1375919840	42.55744626
2.0000000000	-632.1238545320	78.62512649
2.1000000000	-632.0932221670	159.0504008

HMim-CL PES Plot for Me₃NH-Cl

Plot of Total relative energy (kJ/mol) vs Scan coordinate (Â)

This graph shows that when the N-Cl distance is set at 3.2 Â a broad minima occurs, the most stable state is an ion-pair Me₃NH⁺ --- Cl^- and as the proton is pushed to the Cl forming a neutral pair Me₃N --- HCl the energy goes up, and no stable minima forms, rather there is a "shelf" in the PES. The ion-pair forms a doubly ionic H-bond between the Me₃NH⁺ and Cl^-, the neutral-pair forms a normal H-bond between the Me₃N and HCl.

1-methyl-imidazolium chloride A

Calculation data

name of submitted log file	IR_IMIDA_A_OPT.LOG
molecule	1-methyl-imidazolium chloride A
method	RB3LYP
basis set	3-21G(d,p)
final energy	-722.687898
RMS gradient	1.96e-07
point group	C1

Item Table

        Item               Value     Threshold  Converged?
 Maximum Force            0.000000     0.000015     YES
 RMS     Force            0.000000     0.000010     YES
 Maximum Displacement     0.000004     0.000060     YES
 RMS     Displacement     0.000001     0.000040     YES

Low frequencies data

Low frequencies	-5.1397	-2.7750	0.0021	0.0028	0.0030	2.7889
Low frequencies	36.1426	64.4146	80.7977

Optimised molecule image

logfile: Media:IR IMIDA A OPT.LOG

Important Geometric parameters

Optimised bond lengths

r(H-N)(3-5)= 1.1776 Â
r(H-Cl)(3-14)= 1.7193 Â
r(N-Cl)(5-14)= 2.8914 Â
r(C-H)(1-2)= 1.07478 Â
r(C-H)(12-13)= 1.07388 Â
r(N-C)(5-12)= 1.3895 Â
r(C-N)(5-1)= 1.33207 Â

Scan for 1-methyl-imidazolium chloride A

Raw data

Data Table

Scan Coordinate Â	Total Energy (Hartrees)	Relative Total Energy kJ mol -1
0.8000000000	-722.5958117430	219.3908443
0.9000000000	-722.6503978370	76.07505448
1.0000000000	-722.6727650690	17.34988686
1.1000000000	-722.6793732910	0
1.2000000000	-722.6792906320	0.217021205
1.3000000000	-722.6772128850	5.672145953
1.4000000000	-722.6753243630	10.63046046
1.5000000000	-722.6744432310	12.94387253
1.6000000000	-722.6746286640	12.45701819
1.7000000000	-722.6753546960	10.55082117
1.8000000000	-722.6753493340	10.5648991
1.9000000000	-722.6721372800	18.99814688
2.0000000000	-722.6613011090	47.44851384
2.1000000000	-722.6354465340	115.3297005

Formal Scan Graph for 1-methyl-imidazolium chloride A

1-methyl-imidazolium chloride B

Calculation data

name of submitted log file	IR_IMIDA_B_OPT.LOG
molecule	1-methyl-imidazolium chloride B
method	RB3LYP
basis set	3-21G(d,p)
final energy	-722.6662
RMS gradient	3.291e-06
point group	C1

Item Table

         Item               Value     Threshold  Converged?
 Maximum Force            0.000006     0.000450     YES
 RMS     Force            0.000002     0.000300     YES
 Maximum Displacement     0.000443     0.001800     YES
 RMS     Displacement     0.000078     0.001200     YES

Low frequencies data

Low frequencies	-5.0731	-2.6203	-0.0031	-0.0021	0.0024	1.7049
Low frequencies	45.4247	162.0729	198.7836

Optimised molecule image and Jmol rotateable molecule

logfile: Media:IR IMIDA B OPT.LOG

Important Geometric parameters

Optimised bond lengths

r(H-N)(7-3)= 1.10445 Â
r(H-Cl)(7-14)= 2.13423 Â
r(H-Cl)(13-14)= 2.27699 Â
r(N-Cl)(8-14)= 3.64968 Â
r(C-H)(3-7)= 1.10446 Â
r(C-H)(10-13)= 1.10623 Â
r(N-C)(8-10)= 1.496 Â
r(C-N)(3-8)= 1.40206 Â

1-methyl-imidazolium chloride C

Calculation data

name of submitted log file	IR_IMIDA_C_OPT.LOG
molecule	1-methyl-imidazolium chloride C
method	RB3LYP
basis set	3-21G(d,p)
final energy	-761.77953
RMS gradient	2.192e-06
point group	C1

Item Table

         Item               Value     Threshold  Converged?
 Maximum Force            0.000006     0.000450     YES
 RMS     Force            0.000002     0.000300     YES
 Maximum Displacement     0.000110     0.001800     YES
 RMS     Displacement     0.000036     0.001200     YES

Low frequencies data

Low frequencies	--3.6719	-3.0923	-0.0036	-0.0031	-0.0022	2.2057
Low frequencies	52.1748	102.5801	107.1376

Optimised molecule image

logfile: Media:IR IMIDA C OPT.LOG

Important Geometric parameters

Optimised bond lengths

r(H-C)(4-1)= 1.11785 Â
r(H-Cl)(4-17)= 2.03013 Â
r(H-Cl)(11-17)= 2.41692 Â
r(N-Cl)(7-17)= 3.66575 Â
r(C-H)(9-11)= 1.10140 Â
r(N-C)(7-9)= 1.49021 Â
r(C-N)(1-7)= 1.34794 Â

Ionic liquid ion pair (1-methyl-imidazolium chloride (HMim-Cl) A, B, and C)

Optimised H--Cl bond lengths

Molecule Name	HMim-Cl A	HMim-Cl B	HMim-Cl C
Bond distance (Â)	NH3 Molecule Calculation data name of submitted log file IRobertson_nh3_optf_pop.log molecule NH3 method RB3LYP basis set 6-31G(d,p) final energy -56.557769 RMS gradient 1.53e-07 point group C3v Item Table Item Value Threshold Converged? Maximum Force 0.000000 0.000015 YES RMS Force 0.000000 0.000010 YES Maximum Displacement 0.000003 0.000060 YES RMS Displacement 0.000001 0.000040 YES Low frequencies data Low frequencies -5.6864 -3.6131 -3.6124 0.0017 0.0048 0.0162 Low frequencies 1089.3674 1693.9284 1693.9284 Optimised molecule image Jmol rotateable molecule logfile: Media:IROBERTSON_NH3_OPTF_POP.LOG optimised NH molecule Important geometric parameters Optimised bond distance and angle for NH3 r(N-H)=1.02Â θ(H-N-H)=106° Vibrational data Mode 1 2 3 4 5 6 Wavenumber (cm-1) 1089 1694 1694 3461 3590 3590 Symmetry A1 E E A1 E E Intensity (arbitrary) 145 14 14 1 0 0 Optimised molecule image with charges Atoms N H Charge -1.13 0.38 N2F2 Molecule Calculation data name of submitted log file IJR_N2F2_C2V_OPTF.LOG molecule N2F2 method RB3LYP basis set 6-31G(d,p) final energy -309.01241 RMS gradient 3.17e-07 point group C2V Item Table Item Value Threshold Converged? Maximum Force 0.000000 0.000015 YES RMS Force 0.000000 0.000010 YES Maximum Displacement 0.000001 0.000060 YES RMS Displacement 0.000000 0.000040 YES Optimised N2F2 molecule Optimised N2F2 molecule image Jmol rotatable molecule logfile: Media:IJR_N2F2_C2V_OPTF.LOG optimised NF molecule Important geometric parameters Optimised bond distance and angle for N2F2 r(N-F)=1.39Â r(N-N)=1.22Â θ(F-N-N)=114° θ(F-N-N-F)=0° Vibrational Data and analysis Mode 1 2 3 4 5 6 Wavenumber (cm-1) 348 561 772 949 987 1637 Symmetry A1 A2 B2 A1 B2 A1 Intensity (arbitrary) 1 0 75 75 81 21 Which vibration is the asymmetric N-F stretch? Vibration 3 is asymmetric. What is the nature of the highest energy vibration? It is an N-N stretching vibration N2F2 Spectrum IR Analysis How many vibrations are expected from the 3N-6 rule? We would expect there to be 6 vibrations (3(4) - 6 = 6) Why are there only 4 peaks in the IR spectrum? The A1 347.88 cm-1 and the A2 561.25 cm-1 modes have essentially no intensity, as both of these modes must have no dipole change. Therefore only the remaining 4 modes can be observed in the IR spectrum as peaks. Low frequencies data Low frequencies -0.0024 -0.0016 -0.0014 3.3364 4.3775 5.1348 Low frequencies 347.8779 561.2478 771.6088 Optimised molecule image with charges Atoms N F Charge 0.26 -0.26 Molecular Orbital analysis N2F2 MO 9 Which MOs are core orbital MOs? The core MOs are the first four MOs 1-4 with low lying energy.