Directory UMM :wiley:Public:journals:jcc:suppmat:17:
0.8
RHF/6-31G**
MM3(94)
MM2(91)
Relative Energy (kcal/mol)
0.6
0.4
0.2
0.0
0
30
60
90
120
150
180
Torsion Angle (Degrees), (=C-N+-C-H)
Supplemental Figure 1. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Profiles for N-methylpyridinium.
RHF/6-31G**
MM3(94)
MM2(91)
3.0
Relative Energy (kcal/mol)
2.5
2.0
1.5
1.0
0.5
0.0
0
30
60
90
120
150
180
Torsion Angle (Degrees), (=C-N+-C-C)
Supplemental Figure 2. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Profiles for N-n-propylpyridinium.
6
RHF/6-31G**
MM3(94)
MM2(91)
Relative Energy (kcal/mol)
5
4
3
2
1
0
0
30
60
90
120
150
180
Torsion Angle (Degrees), (=C-N+-C-C)
Supplemental Figure 3. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Profiles for N-isopropylpyridinium.
11
RHF/6-31G**
MM3(94)
MM2(91)
10
9
Relative Energy (kcal/mol)
8
7
6
5
4
3
2
1
0
0
30
60
90
120
150
180
Torsion Angle (Degrees), (=C-N+-C-C)
Supplemental Figure 4. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Profiles for s-trans-N-ethyl-N-vinylmethyleneammonium.
12
RHF/6-31G**
MM3(94)
MM2(94)
Relative Energy (kcal/mol)
10
8
6
4
2
0
0
30
60
90
120
150
180
Torsion Angle (Degrees), (=C-N+-C-C)
Supplemental Figure 5. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Profiles for s-trans-N-n-propyl-N-vinylmethyleneammonium.
12
RHF/6-31G**
MM3(94)
MM2(91)
Relative Energy (kcal/mol)
10
8
6
4
2
0
0
30
60
90
120
150
180
Torsion Angle (Degrees), (=C-N+-C-C)
Supplemental Figure 6. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Profiles for s-trans-N-isopropyl-N-vinylmethyleneammonium.
Supplemental Table 1. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
Pyridinium.
H8
H7
C3
H9
C2
C4
N+ 1 H11
C5
C6
H10
Bond
N+(1) - C(2)
N+(1) - C(6)
N+(1) - H(11)
RHF/6-31G**a
1.3638
1.3639
1.0121
MM2 (91)b
1.3520
1.3521
1.0128
RMS Diffc
Bond Angle
C(2) - N+(1) - C(6)
C(2) - N+(1) - H(11)
C(6) - N+(1) - H(11)
N+(1) - C(2) - C(3)
N+(1) - C(2) - H(7)
N+(1) - C(6) - C(5)
N+(1) - C(6) - H(12)
RHF/6-31G**d
123.139
118.428
118.428
119.682
116.761
119.682
116.761
MM2 (91)e
122.742
118.629
118.629
119.725
116.376
119.727
116.375
RMS Diff
________________
H12
Difference
-0.0118
-0.0118
0.0007
MM3(94)b
1.3546
1.3546
1.0140
0.0077
Difference
-0.397
0.201
0.201
0.043
-0.385
0.045
-0.386
0.212
Difference
-0.0092
-0.0093
0.0019
0.0065
MM3(94)e
124.048
117.976
117.976
119.443
116.091
118.443
116.091
Difference
0.909
-0.452
-0.452
-1.239
-0.670
-1.239
-0.670
0.659
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3 (94)
g
calculations of the pyridine and ethane structures.
b MM2 (91) and MM3 (94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3 (94) structures of pyridine and
ethane.
eMM2 (91) and MM3 (94) bond angles are given in degrees (°).
Supplemental Table 2. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
N-ethylpyridinium
H8
H7
C3
H9
N+ 1
RHF/6-31G**a
1.3641
1.3641
1.5037
RHF/6-31G**d
120.610
119.694
119.667
121.198
116.528
121.198
116.521
111.709
106.838
106.795
MM2(91)b
1.3650
1.3650
1.4989
MM2(91)e
120.391
119.616
119.490
120.743
117.294
120.746
117.274
111.426
107.618
107.538
RMS Diff
________________
C11
H14
H15
RMS Diffc
Bond Angle
C(2) - N+(1) - C(6)
C(2) - N+(1) - C(11)
C(6) - N+ (1) - C(11)
N+(1) - C(2) - C(3)
N+(1) - C(2) - H(7)
N+(1) - C(6) - C(5)
N+(1) - C(6) - H(15)
N+(1) - C(11) - C(12)
N+(1) - C(11) - H(13)
N+(1) - C(11) - H(14)
C12 H18
H13
C6
H10
Bond
N+(1) - C(2)
N+(1) - C(6)
N+(1) - C(11)
H16
C2
C4
C5
H17
Difference
0.0009
0.0009
-0.0048
MM3(94)b
1.3646
1.3645
1.5062
0.0060
Difference
-0.219
-0.078
-0.177
-0.455
0.766
-0.452
0.753
-0.283
0.780
0.743
0.439
Difference
0.0005
0.0004
0.0025
0.0043
MM3(94)e
120.106
119.944
119.944
120.679
115.584
120.679
115.584
110.976
106.988
106.988
Difference
-0.504
0.250
0.277
-0.519
-0.944
-0.519
-0.937
-0.733
0.150
0.193
0.469
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the pyridine and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of pyridine and
ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 3. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
N-n-propylpyridinium.
H8
H7
C3
H9
C2
C4
N+ 1
C5
H10
Bond
N+(1) - C(2)
N+(1) - C(6)
N+(1) - C(13)
H18
H17
RHF/6-31G**a
1.3640
1.3640
1.5028
RHF/6-31G**d
120.585
119.700
119.700
121.216
116.500
121.216
116.500
106.910
111.840
106.900
C6
C15
H21
C13
H20
H16
H11
MM2(91)b
1.3650
1.3650
1.4990
MM2(91)e
120.395
119.461
119.592
120.748
117.280
120.740
117.288
107.517
111.410
107.457
RMS Diff
________________
C14
H12
RMS Diffc
Bond Angle
C(2) - N+(1) - C(6)
C(2) - N+(1) - C(13)
C(6) - N+(1) - C(13)
N+(1) - C(2) - C(3)
N+(1) - C(2) - H(7)
N+(1) - C(6) - C(5)
N+(1) - C(6) - H(11)
N+(1) - C(13) - H(12)
N+(1) - C(13) - C(14)
N+(1) - C(13) - H(16)
H19
Difference
0.0010
0.0010
-0.0038
MM3(94)b
1.3644
1.3644
1.5123
0.0056
Difference
-0.190
-0.239
-0.108
-0.468
0.780
-0.476
0.788
0.607
-0.430
0.557
0.435
Difference
0.0004
0.0004
0.0095
0.0051
MM3(94)e
120.123
119.936
119.936
120.672
115.570
120.672
115.570
106.871
111.011
106.871
Difference
-0.462
0.236
0.236
-0.544
-0.930
-0.544
-0.930
-0.039
-0.829
-0.029
0.488
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the pyridine and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of pyridine and
ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 4. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
N-isopropylpyridinium
H8
H7
C3
H9
N+ 1
C6
H10
Bond
N+(1) - C(2)
N+(1) - C(6)
N+(1) - C(12)
RHF/6-31G**a
1.3631
1.3653
1.5217
RHF/6-31G**d
120.178
119.731
120.091
121.483
116.676
121.483
116.789
110.377
110.352
104.112
MM2(91)b
1.3666
1.3660
1.5060
MM2(91)e
120.120
120.175
119.705
120.836
117.770
120.894
117.573
111.471
111.439
107.023
RMS Diff
________________
C13 H18
C12
H21
H11 H
20
RMS Diffc
Bond Angle
C(2) - N+(1) - C(6)
C(2) - N+(1) - C(12)
C(6) - N+(1) - C(12)
N+(1) - C(2) - C(3)
N+(1) - C(2) - H(7)
N+(1) - C(6) - C(5)
N+(1) - C(6) - H(11)
N+(1) - C(12) - C(13)
N+(1) - C(12) - C(14)
N+(1) - C(12) - C(14)
H16
C2
C4
C5
H17
H15
C14
H19
Difference
0.0035
0.0007
-0.0157
MM3(94)b
1.3652
1.3662
1.5222
0.0069
Difference
-0.058
0.444
-0.386
-0.647
1.094
-0.589
0.784
1.094
1.087
2.911
0.958
Difference
0.0021
0.0009
0.0005
0.0042
MM3(94)e
119.710
120.038
120.251
120.873
115.912
120.907
115.817
110.633
110.633
105.585
Difference
-0.468
0.307
0.160
-0.610
-0.764
-0.576
-0.972
0.256
0.281
1.473
0.571
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the pyridine and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of pyridine and
ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 5. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
s-trans- N-vinylmethyleneammonium
H9
H10
H7
C4
C3
N+ 2
H8
Bond
C(1) - N+(2)
N+(2) - C(3)
N+(2) - H(7)
RHF/6-31G**a
1.3003
1.4506
1.0210
MM2(91)b
1.2892
1.4390
1.0130
RMS Diffc
Bond Angle
N+(2) - C(1) - H(5)
N+(2) - C(1) - H(6)
C(1) - N+(2) - C(3)
C(1) - N+(2) - H(7)
C(3) - N+(2) - H(7)
N+(2) - C(3) - C(4)
N+(2) - C(3) - H(8)
RHF/6-31G**d
119.988
119.699
126.019
117.853
116.128
120.840
114.206
MM2(91)e
118.943
117.269
126.305
117.126
116.569
121.153
116.695
RMS Diff
________________
C1
H5
H6
Difference
-0.0111
-0.0116
-0.0080
MM3(94)
1.2925
1.4450
1.0141
0.0082
Difference
-1.045
-2.430
0.286
-0.727
0.441
0.313
2.489
1.251
Difference
-0.0078
-0.0056
-0.0069
0.0062
MM3(94)
118.089
117.606
127.437
116.203
116.361
121.858
114.703
Difference
-1.899
-2.093
1.418
-1.650
0.233
1.018
0.497
1.250
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the pyridine and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of pyridine and
ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 6. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
s-trans- N-ethyl-N-vinylmethyleneammonium.
H16
H10
H6 H11
H7
C1
C2
C9
N+ 3
H8
Bond
C(2) - N+(3)
N+(3) - C(4)
N+(3) - C(5)
RHF/6-31G**a
1.4607
1.4995
1.3006
MM2(91)b
1.4661
1.5040
1.3015
RMS Diffc
Bond Angle
C(1) - C(2) - N+(3)
N+(3) - C(2) - H(8)
C(2) - N+(3) - C(4)
C(2) - N+(3) - C(5)
C(4) - N+(3) - C(5)
N+(3) - C(4) - C(9)
N+(3) - C(4) - H(10)
N+(3) - C(4) - H(11)
N+(3) - C(5) - H(12)
N+(3) - C(5) - H(13)
RHF/6-31G**d
124.771
112.916
120.379
119.470
120.145
111.840
106.385
111.187
120.363
120.098
MM2(91)e
124.360
115.858
120.038
121.277
118.568
111.923
108.359
107.605
118.802
119.494
RMS Diff
________________
H15
H14
C4
C5
H12
H13
Difference
0.0054
0.0045
0.0009
MM3(94)b
1.4596
1.5086
1.3011
0.0067
Difference
-0.411
2.942
-0.341
1.807
-1.577
0.083
1.974
0.776
-1.561
-0.604
1.354
Difference
-0.0011
0.0091
0.0005
0.0056
MM3(94)e
124.772
113.944
120.586
120.110
119.303
111.415
107.268
107.026
118.737
118.387
Difference
0.001
1.028
0.207
0.640
-0.842
-0.425
0.883
0.197
-1.626
-1.711
0.856
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the N-vinyl-2-ethylidenimine (s-trans) and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of N-vinyl-2ethylidenimine (s-trans) and ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 7. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
s-trans-N-n-propyl-N-vinylmethyleneammonium.
H15
H16
H12
H9
C4
C1
N+ 3
H10
Bond
C(2) - N+(3)
N+(3) - C(4)
N+(3) - C(7)
RHF/6-31G**a
1.4604
1.4987
1.3005
MM2(91)b
1.4662
1.5041
1.3015
RMS Diffc
Bond Angle
C(1) - C(2) - N+(3)
N+(3) - C(2) - H(10)
C(2) - N+(3) - C(4)
C(2) - N+(3) - C(7)
C(4) - N+(3) - C(7)
N+(3) - C(4) - C(5)
N+(3) - C(4) - H(11)
N+(3) - C(4) - H(12)
N+(3) - C(7) - H(18)
N+(3) - C(7) - H(19)
RHF/6-31G**d
124.807
112.911
120.471
119.420
120.102
112.011
106.451
106.917
120.054
120.393
MM2(91)e
124.363
115.854
120.037
121.297
118.552
111.966
108.249
107.502
119.474
118.805
RMS Diff
________________
H17
C5
H8 H11
C2
C6
H13
H14
C7
H18
H19
Difference
0.0058
0.0054
0.0010
MM3(94)b
1.4595
1.5147
1.3010
0.0063
Difference
-0.444
2.943
-0.434
1.877
-1.550
-0.045
1.798
0.585
-0.580
-1.588
1.283
Difference
-0.0009
0.0160
0.0005
0.0063
MM3(94)e
124.757
113.947
120.590
120.140
119.269
111.444
107.148
106.916
118.348
118.747
Difference
-0.050
1.036
0.119
0.720
-0.833
-0.567
0.697
-0.001
-1.706
-1.646
0.819
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the N-vinyl-2-ethylidenimine (s-trans) and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of N-vinyl-2ethylidenimine (s-trans) and ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 8. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
s-trans- N-isopropyl-N-vinylmethyleneammonium.
H19
H16
H6 H10
H17 C9
H15
C4
H14
C1
N+ 3
H18
H7
C11
C2
H8
Bond
C(2) - N+(3)
N+(3) - C(4)
N+(3) - C(5)
RHF/6-31G**a
1.4624
1.5186
1.3002
MM2(91)b
1.4687
1.5074
1.2975
RMS Diffc
Bond Angle
C(1) - C(2) - N+(3)
N+(3) - C(2) - H(8)
C(2) - N+(3) - C(4)
C(2) - N+(3) - C(5)
C(4) - N+(3) - C(5)
N+(3) - C(4) - C(9)
N+(3) - C(4) - C(10)
N+(3) - C(4) - H(11)
N+(3) - C(5) - H(12)
N+(3) - C(5) - H(13)
RHF/6-31G**d
125.651
112.642
119.713
118.430
121.838
108.960
112.196
103.910
120.125
120.658
MM2(91)e
123.563
115.680
119.535
121.057
119.394
110.952
112.872
106.480
118.527
119.545
RMS Diff
________________
C5
H12
H13
Difference
0.0063
-0.0112
-0.0027
MM3(94)b
1.4631
1.5232
1.2997
0.0078
Difference
-2.088
3.038
-0.178
2.627
-2.444
1.992
0.676
2.570
-1.598
-1.113
1.856
Difference
0.0007
0.0046
-0.0005
0.0060
MM3(94)e
124.494
113.852
120.387
119.539
120.074
110.172
111.722
105.401
118.487
118.743
Difference
-1.157
1.210
0.674
1.109
-1.764
1.212
-0.474
1.491
-1.638
-1.915
1.220
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the N-vinyl-2-ethylidenimine (s-trans) and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of N-vinyl-2ethylidenimine (s-trans) and ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 9. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
s-trans-N-n-butyl-N-vinylmethyleneammonium.
H20
H19
H18
H15
H10 H14
H9
C1
C2
RHF/6-31G**a
1.4602
1.3004
1.4992
RHF/6-31G**d
124.798
112.920
119.414
120.472
120.108
120.401
120.040
112.003
106.393
106.864
MM2(91)b
1.4663
1.3015
1.5041
MM2(91)e
124.363
115.854
121.298
120.042
118.545
118.805
119.474
111.935
108.227
107.489
RMS Diff
________________
H17
H16
N+ 3
RMS Diffc
Bond Angle
C(1) - C(2) - N+(3)
N+(3) - C(2) - H(11)
C(2) - N+(3) - C(4)
C(2) - N+(3) - C(5)
C(4) - N+(3) - C(5)
N+(3) - C(4) - H(12)
N+(3) - C(4) - H(13)
N+(3) - C(5) - C(6)
N+(3) - C(5) - H(14)
N+(3) - C(5) - H(15)
C8 H
22
H21
C6
C5
H11
Bond
C(2) - N+(3)
N+(3) - C(4)
N+(3) - C(5)
C7
C4
H13
H12
Difference
0.0061
0.0011
0.0049
MM3(94)b
1.4595
1.3010
1.5147
0.0062
Difference
-0.435
2.934
1.884
-0.430
-1.563
-1.596
-0.566
-0.068
1.834
0.625
1.242
Difference
-0.0007
0.0006
0.0155
0.0060
MM3(94)e
124.754
113.948
120.145
120.583
119.270
118.747
118.346
111.414
107.146
106.886
Difference
-0.044
1.028
0.731
0.111
-0.838
-1.654
-1.694
-0.589
0.753
0.022
0.794
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the N-vinyl-2-ethylidenimine (s-trans) and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of N-vinyl-2ethylidenimine (s-trans) and ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 10: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for Pyridinium.
RHF/6-31G**
3432.4
3079.0
3077.7
3067.0
3065.6
3048.0
------1635.8
1631.6
1544.1
1482.8
1378.4
1291.7
1197.6
1185.0
1112.6
1052.1
1044.4
1041.5
1016.6
1012.6
1010.5
980.4
883.4
842.0
737.8
652.5
621.2
596.8
395.4
383.1
MM3(94)
3426.2
3081.3
3079.9
3068.9
3065.0
3056.1
1696.7
1638.5
1656.1
1509.8
1455.4
1381.7
1223.8
1203.3
1150.3
------1147.7
978.9
995.8
1092.0
935.5
1026.7
911.7
818.6
851.5
750.4
632.4
581.5
584.5
397.4
425.6
Total of 29 Vibrations
Difference
6.2
-2.3
-2.2
-1.9
0.6
-8.1
-------2.7
-24.5
34.3
27.4
-3.3
67.9
-5.7
34.7
-------95.6
65.5
45.7
-75.4
77.1
-16.2
68.7
64.8
-9.5
-12.6
20.1
39.7
12.3
-2.0
-42.5
RMS: 41.1
Assignment
N+-H stretching
CH2 sym/sym stretch
CH2 sym/asym stretch
CH2 asym/sym stretch
CH2 asym/asym stretch
CH2 sym str + N+-H str
Csp2 -Csp2 asym stretch
N+-Csp2 asym stretch
Csp2 -Csp2 asym stretch
CH2 asym wag
Csp2 -Csp2 asym stretch
CH2 sym wag
CH2 asym wag + N+-H wag
CH2 asym wag
CH2 sym wag
Csp2 -Csp2 stretch
CH2 out-of-plane wag
N+-Csp2 symm stretch
Csp2 -Csp2 asym stretch
CH2 out-of-plane wag
Skeletal bending
CH2 out-of-plane wag
Ring Breathing
CH2 out-of-plane wag
CH2 out-of-plane wag
CH2 out-of-plane bending
CH2 out-of-plane bending
Skeletal bending
Skeletal bending
Ring twisting
Ring deformation
Supplemental Table 11: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for N-methylpyridinium
RHF/6-31G**
3077.6
3075.1
3065.2
3062.7
3048.5
3018.1
3004.9
2916.6
1649.0
------1602.6
1501.7
1491.0
1455.7
1448.6
1428.3
1361.6
1222.1
------1203.3
1177.5
1134.7
1127.9
1107.5
1049.1
1042.5
1021.2
1014.9
1008.2
991.3
880.0
779.6
766.4
664.4
636.6
514.4
438.8
395.6
373.9
193.6
18.7
-------
MM3(94)
3079.2
3075.2
3067.3
3062.0
3055.6
2981.8
2991.6
2869.5
1674.8
1676.6
1617.2
1510.9
1454.0
1385.8
1419.6
1420.9
1299.0
1226.1
1178.6
1177.5
1163.4
------1100.9
------1112.8
980.6
1044.4
1116.1
931.4
996.2
846.1
747.3
771.9
664.8
581.1
509.2
447.8
374.5
406.1
198.1
-------15.9
Total of 36 Vibrations
Difference
-1.6
-0.1
-2.1
0.7
-7.1
36.3
13.3
47.1
-25.8
-------14.6
-9.2
37.0
69.9
29.0
7.4
62.6
-4.0
------25.8
14.1
------27.0
-------63.7
61.9
-23.2
-101.2
76.8
-4.9
33.9
32.3
-5.5
-0.4
55.5
5.2
-9.0
21.1
-32.2
-4.5
------------RMS: 36.9
Assignment
C-H sym/sym stretch
C-H sym/asym stretch
C-H asym/sym stretch
C-H asym/asym stretch
C-H stretch
CH3 asym stretch
CH3 asym stretch
CH3 sym stretch
Csp2 =Csp2 sym stretch
Csp2 =Csp2 + N+-Csp2 asym str
Csp2 =Csp2 + N+-Csp2 asym str
Csp2 =Csp2 + N+-Csp2 sym str
Csp2 =Csp2 + N+-Csp2 asym str
CH3 asym bend
CH3 asym bend (C-H wagging)
CH3 sym bend
C-H sym wag (in-plane)
C-H asym + CH3 wag (in-plane)
CH3 wag + CH out-of-plane bend
C-H asym wag (in-plane)
CH3 stretch + skeletal bend
C-H wag + CH3 rocking
CH3 wagging (out-of-plane)
Csp2 =Csp2 asym stretch
C-H asym wag (out-of-plane)
Csp2 =Csp2-Csp2 bending
Csp2 =Csp2 + N+-Csp2 asym str
C-H asym wag (out-of-plane)
Ring Breathing
C-H sym wag (out-of-plane)
C-H asym wag (out-of-plane)
C-H sym wag (out-of-plane)
Csp2 =Csp2-Csp2 bending
Ring out-of-plane deformation
Ring bending (in-plane)
Ring bending (in-plane)
Ring bending (out-of-plane)
Ring twisting
CH3 in-plane wag
CH3 out-of-plane wag
CH3 torsion
CH3 torsion
Supplemental Table 12: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for N-ethylpyridinium.
RHF/6-31G**
3076.3
3073.9
3064.4
3061.8
3048.0
2992.3
2961.6
2950.6
2938.6
2883.0
1647.4
1603.4
1503.9
1485.3
1471.5
1454.2
------1452.4
1404.7
1363.9
1355.8
1283.9
1202.0
1200.9
1161.8
1141.6
1105.4
1081.6
1048.5
1042.7
------1038.8
1015.1
1008.3
993.1
935.3
880.8
787.1
773.7
739.8
672.8
636.6
536.0
470.4
396.4
379.2
310.2
217.9
129.7
50.7
MM3(94)
3078.6
3076.3
3067.6
3062.2
3055.7
2948.1
2969.9
2970.2
2892.3
2874.0
1678.7
1619.1
1485.7
1676.6
1556.5
1433.0
1459.9
1451.6
1452.6
1353.2
1370.6
------1234.1
1176.7
1190.7
1221.3
1062.5
1026.0
1154.5
------1036.6
1026.0
1116.1
931.0
1000.5
983.0
846.6
787.8
838.0
754.4
665.0
581.2
540.3
459.7
375.3
406.2
329.1
218.8
135.2
58.5
Total of 46 Vibrations
Difference
-2.3
-2.4
-3.2
-0.4
-7.7
44.2
-8.3
-19.6
46.3
9.0
-31.3
-15.7
18.2
-191.3
-85.0
21.2
------0.8
-47.9
10.7
-14.8
-------32.1
24.2
-28.9
-79.7
42.9
55.6
-106.0
------------12.8
-101.0
77.3
-7.4
-47.7
34.2
-0.7
-64.3
-14.6
7.8
55.4
-4.3
10.7
21.1
-27.0
-18.9
-0.9
-5.5
-7.8
RMS: 48.3
Assignment
C-H sym/sym stretch
C-H sym/asym stretch
C-H asym/sym stretch
C-H asym/asym stretch
C-H stretch
CH2 asym stretch
CH3 asym stretch
CH3 asym stretch
CH2 sym stretch
CH3 sym stretch
Csp2 =Csp2 stretch
Csp2 =Csp2 + N+-Csp2 asym str
Csp2 =Csp2 + N+-Csp2 sym str
C-H wag (in-plane)
CH2 + CH3 asym bend
CH2 + CH3 asym bend
CH3 asym bend
CH3 asym bend
CH3 sym bend
C-H sym wag (in-plane)
CH3 + CH2 wag
C-H wag (in-plane) + CH2 wag
C-H wag (in-plane)
C-H asym wag (in-plane)
N+-Csp3 stretch
C-H wag + CH2 wag (in-plane)
Csp2 =Csp2 stretch
CH3 rock
C-H wag (out-of-plane)
Csp2 =Csp2-Csp2(N+) asym bend
C-H asym wag (out-of-plane)
Csp2 =Csp2 + N+-Csp2 sym str
C-H asym wag (out-of-plane)
Ring breathing
C-H asym wag (out-of-plane)
Ring breathing + CH3 rock
C-H asym wag (out-of-plane)
C-H sym wag (out-of-plane)
CH2 + CH3 wag
Ring bending (Csp2 =Csp2-Csp2)
Ring out-of-plane deformation
Ring bending
Ring bending
Ring bending (Csp2 -N+=Csp2)
Ring twisting
Ethyl in-plane bending
Ethyl bending + ring bending
CH3 torsion
Ethyl bending
Ethyl torsion
Supplemental Table 13: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for N-n-propylpyridinium
RHF/6-31G**
3076.8
3074.3
3064.6
3062.0
3047.8
2985.0
2956.3
2938.4
2932.5
2909.6
2876.6
2875.1
1647.7
1603.4
1503.5
1485.0
1476.2
1463.0
1462.9
1455.3
------1403.7
1379.8
1363.6
1305.6
1299.6
1261.3
1200.9
1196.7
1160.0
1145.3
1104.7
1098.9
1048.1
1043.8
1042.9
1015.0
1008.3
994.3
993.7
881.0
876.6
860.3
794.2
------771.6
725.3
673.2
636.7
578.0
MM3(94)
3078.7
3076.5
3067.6
3062.3
3055.7
2949.4
2968.6
2970.2
2891.3
2924.9
2867.6
2881.3
1679.5
1619.2
1487.8
1676.6
1458.3
1456.9
1453.8
1439.1
1452.9
1395.4
1569.1
1357.3
1351.6
1224.6
1240.2
1175.5
1221.9
1185.2
1033.7
------1060.1
1155.0
1058.8
981.2
1116.2
931.7
1015.4
993.0
846.7
899.7
902.6
762.8
803.1
665.2
787.0
------581.2
568.4
Difference
-1.9
-2.2
-3.0
-0.3
-7.8
35.6
-12.3
-31.8
41.2
-15.3
9.0
-6.2
-31.8
-15.8
15.7
-191.6
17.9
6.0
9.1
16.2
------8.3
-189.3
6.3
-46.0
75.0
21.1
25.4
-25.2
-25.2
111.6
------38.8
-106.9
-15.0
61.7
-101.2
76.6
-21.1
0.7
34.3
-23.1
-42.3
31.4
------106.4
-61.7
------55.5
9.6
Assignment
C-H sym/sym stretch
C-H sym/asym stretch
C-H asym/sym stretch
C-H asym/asym stretch
C-H stretch
CH2 asym stretch
CH3 asym stretch
CH3 asym stretch
CH2 sym stretch
CH2 asym stretch
CH2 sym stretch
CH3 sym stretch
Csp2 =Csp2 stretch
Csp2 =Csp2 + N+-Csp2 asym str
Csp2 =Csp2 + N+-Csp2 sym str
Csp2 =Csp2 + N+-Csp2 asym str
CH2 + CH3 asym bend
CH3 asym bend
CH2 + CH3 asym bend
CH2 + CH3 asym bend
CH2 + CH3 asym bend
CH3 wag
CH2 asym wag
C-H sym wag (in-plane)
CH2 asym wag
CH2 sym wag
CH2 asym wag
C-H wag (in-plane)
C-H asym wag (in-plane)
N+-Csp3 stretch
C-H asym wag (in-plane)
C-H sym wag (in-plane)
CH2 -CH2 stretch
C-H asym bend (out-of-plane)
C-H sym wag (in-plane)
Ring bending (Csp2 =Csp2-Csp2)
C-H wag (out-of-plane)
Ring breathing
C-H wag (out-of-plane)
Csp3 -Csp3-Csp3 bending
C-H sym wag (out-of-plane)
Csp3 -Csp3-Csp3 bending
CH2 + CH3 bending
Ring deformation (out-of-plane)
Ring deformation (in-plane)
C-H sym wag (out-of-plane)
CH2 twist
N+ out-of-plane bend
Ring deformation (in-plane)
Ring deformation (in-plane)
Supplemental Table 13: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for N-n-propylpyridinium (continued)
RHF/6-31G**
468.8
396.6
372.5
301.8
266.3
225.5
99.5
83.7
49.0
MM3(94)
461.5
375.0
397.1
300.3
295.3
227.5
106.2
50.3
57.1
Total of 55 Vibrations
Difference
7.3
21.6
-24.6
1.5
-29.0
-2.0
-6.8
33.4
-8.1
RMS: 54.2
Assignment
Ring deformation (out-of-plane)
Ring twisting
CH2 wag
CH3 wag
Propyl wag
CH3 twisting
CH2 -CH2 bending
CH2 -CH2 torsion
Propyl torsion
Supplemental Table 14: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for N-isopropylpyridinium
RHF/6-31G**
3090.8
3078.7
3066.1
3063.0
3047.8
2965.5
2962.2
2959.5
2950.4
2941.7
2885.5
2882.2
1645.7
1603.4
------1500.2
1485.9
1466.8
1462.9
1454.0
1445.9
1415.4
1397.6
1380.7
1338.5
1326.9
1203.7
1201.7
1175.7
1143.6
1122.5
1108.8
1095.0
1048.4
1046.7
1039.3
1016.1
1006.6
994.8
926.1
918.6
879.7
860.9
790.0
712.0
675.4
635.7
547.1
506.0
453.3
MM3(94)
3088.2
3079.5
3068.7
3062.7
3055.9
2977.0
2969.6
2968.1
2976.2
2930.7
2879.0
2880.2
1675.8
1628.8
1680.9
1496.6
1553.4
1471.6
1469.4
1459.3
1457.0
1409.0
1443.8
1431.2
1287.0
1343.2
1184.7
1227.3
1091.2
1211.3
1092.1
1037.2
1032.5
1160.0
974.1
930.1
1116.3
------1009.5
940.7
971.1
847.6
870.1
782.0
737.6
665.9
587.8
563.3
481.7
466.3
Difference
2.6
-0.8
-2.6
0.3
-8.1
-11.5
-7.4
-8.6
-25.8
11.0
6.5
2.1
-30.1
-25.4
------3.6
-67.5
-4.8
-6.5
-5.3
-11.1
6.4
-46.2
-50.5
51.5
-16.3
19.0
-25.6
84.5
-67.7
30.4
71.6
62.5
-111.6
72.6
109.2
-100.2
-------14.7
-14.6
-52.5
32.1
-9.2
8.0
-25.6
9.5
47.9
-16.2
24.3
-13.0
Assignment
C-H sym/sym stretch
C-H sym/asym stretch
C-H asym/sym stretch
C-H asym/asym stretch
C-H stretch
CH3 sym/asym stretch
CH3 sym/asym stretch
CH3 asym/asym stretch
CH3 asym/asym stretch
C-H isopropyl stretch
CH3 sym/sym stretch
CH3 asym/sym stretch
Csp2 =Csp2 stretch
Csp2 =Csp2 + N+-Csp2 asym str
C-H wag (in-plane)
Csp2 =Csp2 + N+-Csp2 sym str
Csp2 =Csp2 + N+-Csp2 asym str
CH3 sym/asym bending
CH3 sym/asym bending
CH3 asym/asym bending
CH3 asym/asym bending
CH3 sym/sym bending
CH3 asym/sym bending
C-H wag (in-plane)
C-H isopropyl wag
C-H isopropyl wag
C-H asym wag (in-plane)
C-H asym wag (in-plane)
C-H asym wag (in-plane)
N+-Csp2 stretch
CH3 asym stretch
Ring bending (Csp2 =Csp2-Csp2)
Ring bending (Csp2 =Csp2-Csp2)
C-H wag (out-of-plane)
Ring bending (Csp2 =Csp2-Csp2)
Ring deformation (in-plane)
C-H wag (out-of-plane)
Ring breathing
C-H wag (out-of-plane)
CH3 asym wag
CH3 asym wag
C-H wag (out-of-plane)
CH3 sym wag
C-H wag (out-of-plane)
Ring deformation (in-plane)
C-H wag (out-of-plane)
Ring deformation (in-plane)
Isopropyl deformation
Ring deformation (out-of-plane)
H3C-CH-CH3 bending
Supplemental Table 14: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for N-isopropylpyridinium (continued)
RHF/6-31G**
398.6
322.0
297.2
254.0
226.1
222.8
121.1
43.6
MM3(94)
379.9
344.7
302.7
237.1
255.5
233.5
125.6
55.7
Total of 56 Vibrations
Difference
18.7
-22.7
-5.5
16.9
-29.4
-10.7
-4.5
-12.1
RMS: 39.7
Assignment
Ring twisting
CH3 asym twisting
CH3 sym twisting
CH3 torsion (sym)
Isopropyl rocking
CH3 torsion (asym)
Isopropyl wag
Isopropyl torsion
Supplemental Table 15: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-vinylmethyleneammonium
RHF/6-31G**
3387.5
3113.2
3096.2
3068.0
3002.8
3001.8
1724.9
1663.4
1487.7
1409.4
1389.1
1302.7
1213.5
1137.2
1039.7
1028.3
1021.0
940.5
848.4
747.4
527.8
510.5
314.6
129.6
MM3(94)
3422.4
3135.0
3112.7
3069.4
3021.8
3014.1
1747.6
1589.1
1426.7
1413.5
1241.2
1195.4
1147.9
1134.6
997.1
1071.2
1051.5
994.0
864.5
812.4
500.1
581.3
352.8
139.2
Total of 24 Vibrations
Difference
-34.9
-21.8
-16.5
-1.4
-19.0
-12.3
-22.7
74.3
61.0
-4.1
147.9
107.3
65.6
2.6
42.6
-42.9
-30.5
-53.5
-16.1
-65.0
27.7
-70.8
-38.3
-9.6
RMS: 53.7
Assignment
N+-H stretching
CH2 asym stretch
CH2 asym stretch
C-H stretch
CH2 sym stretch
CH2 sym stretch
N+-Csp2 stretch
Csp2 -Csp2 stretch
CH2 scissor
N+-H wag
CH2 wag
C-H wag
CH2 wag
CH2 out-of-plane wag
CH2 in-plane wag
CH2 out-of-plane wag
CH2 out-of-plane wag
N+-H + CH 2 out-of-plane wag
CH2 in-plane wag
Vinyl wag
N+-Csp2=Csp2 bend
CH2 twist
Csp2 -N+-Csp2 bend
Skeletal torsion
Supplemental Table 16: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-methyl-N-vinylmethyleneammonium
RHF/6-31G**
3115.3
3105.2
3065.0
3023.3
3020.4
3010.7
3007.6
2919.4
1720.4
1669.1
1487.8
1446.7
1444.1
1427.8
1401.3
1344.0
------1300.4
1137.5
MM3(94)
3137.2
3118.1
3059.5
3027.2
2990.2
2985.0
3017.9
2870.5
1669.6
1553.5
1410.1
1437.2
1440.0
------1471.9
1294.9
1285.7
1234.0
1245.5
Difference
-21.9
-12.9
5.5
-3.9
30.2
25.7
-10.3
48.9
50.8
115.6
77.7
9.5
4.1
-------70.6
49.1
------66.4
-108.0
1123.1
1142.8
-19.7
1118.4
1065.7
1023.5
961.6
1099.4
1047.7
1124.4
1069.4
19.0
18.0
-100.9
-107.8
932.3
------759.8
753.6
631.0
534.7
473.2
393.0
308.2
216.5
107.3
905.0
968.4
723.2
783.4
------539.8
501.4
492.2
325.1
256.0
96.9
Total of 31 Vibrations
27.3
------36.6
-29.8
-------5.1
-28.2
-99.2
-16.9
-39.5
10.4
RMS: 53.5
Assignment
CH2 asym stretch
CH2 asym stretch
C-H stretch
CH2 sym + CH3 asym stretch
CH2 sym str + CH3 asym str
CH3 asym stretch
CH2 sym stretch
CH3 sym stretch
N+=Csp2 stretch
Csp2 =Csp2 stretch
CH2 scissor + CH3 asym bend
CH2 asym bend + CH2 scissor
CH3 asym bend
CH3 sym bend
CH2 scissor
C-H wag (in-plane) + N+-CH3 str
CH2 scissor
C-H wag (in-plane) + N+-CH3 str
CH3 rock + CH2 wag (out-ofplane)
CH2 wag (out-of-plane) + CH3
rock
CH3 wag
CH2 asym wag (in-plane)
CH2 wag (out-of-plane)
C-H wag (out-of-plane) + CH2
twist
CH2 sym wag (in-plane)
CH2 twist
CH2 sym twist
N+-Csp2 + N+-CH3 stretch
CH2 twist
Csp2 =Csp2-N+ bend
Csp2 -N+=Csp2 bend
N+ out-of-plane bend
Csp2 =Csp2-N+ bend
CH3 torsion
Skeletal torsion
Supplemental Table 17: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-ethyl-N-vinylmethyleneammonium
RHF/6-31G**
3112.1
3105.9
3061.5
3022.7
3006.9
3002.2
2973.4
2959.6
2947.9
2891.2
1716.1
1669.0
1491.8
1462.8
1458.3
1452.0
1405.7
1404.0
1361.6
1342.6
1305.3
1248.9
1137.9
1127.7
1085.0
1067.3
1021.3
967.0
MM3(94)
3137.2
3121.2
3058.0
3029.3
3017.8
2954.6
2977.2
2969.3
2897.5
2877.6
1672.9
1586.9
1468.7
1526.2
1456.1
1460.2
1442.5
1387.1
1314.1
1370.3
1240.0
1210.8
1065.0
1232.4
1042.9
1027.2
1123.4
1077.5
961.1
890.4
786.7
762.1
709.9
655.9
535.4
472.4
465.1
330.1
241.0
200.0
119.8
87.7
996.3
897.6
854.9
942.2
776.5
728.8
549.1
528.4
494.1
352.8
272.1
210.5
134.4
82.3
Total of 42 Vibrations
Difference
-25.1
-15.3
3.5
-6.7
-10.9
47.6
-3.8
-9.7
50.4
13.7
43.2
82.1
23.1
-63.4
2.2
-8.2
-36.8
16.9
47.5
-27.7
65.3
38.1
72.9
-104.7
42.0
40.1
-102.1
-110.5
-35.2
-7.2
-68.2
-180.1
-66.6
-72.9
-13.7
-56.0
-29.0
-22.7
-31.1
-10.5
-14.6
5.4
RMS: 54.8
Assignment
CH2 asym stretch
CH2 asym stretch
C-H stretch
CH2 sym stretch
CH2 sym str + Csp3 -H asym str
Csp3 -H asym str
CH3 asym stretch
CH3 asym stretch
Csp3 -H sym stretch
CH3 sym stretch
N+-Csp2 + Csp2=Csp2 stretch
Csp2 =Csp2 + N+-Csp2 stretch
CH2 scissor
CH3 asym bend + CH2 scissor
CH3 asym bend + CH2 scissor
CH3 asym bend
CH3 sym bend + CH2 scissor
CH3 sym bend + CH2 scissor
CH2 (ethyl) asym bend
C-H wag + CH2 asym bend
C-H wag + CH2 (ethyl) wag
CH2 (ethyl) + CH2 wag (in-plane)
CH3 rock
CH2 wag (out-of-plane)
CH3 wag
CH2 asym wag (in-plane)
CH2 wag (out-of-plane)
C-H wag (out-of-plane) + CH2
twist
Csp3 -Csp3 stretch
CH2 sym wag (in-plane)
Ethyl wag
CH2 twisting
Csp2 -N+ str + CH3 rock
CH2 twist
Csp2 =N+-Csp2 bend
N+ out-of-plane bend
CH2 wag (in-plane)
Csp2 =Csp2-N+ bend
Csp3 -Csp3-N+ bend
CH3 torsion
Ethyl torsion
Skeletal torsion
Supplemental Table 18: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-n-propyl-N-vinylmethyleneammonium
RHF/6-31G**
3112.4
3106.2
3061.3
3022.7
3006.7
2997.0
2958.2
2945.3
2941.1
2925.0
2887.5
2875.6
1716.1
1669.2
1491.2
1473.7
1463.0
1458.5
------1457.5
1404.5
1404.0
1380.0
1347.6
1314.5
1297.2
1290.0
1228.8
1145.4
1126.5
1099.1
1067.9
1020.2
------991.6
965.5
926.4
878.8
866.1
766.8
758.0
728.2
648.4
549.0
MM3(94)
3137.4
3121.1
3058.1
3029.2
3017.9
2956.1
2968.6
2970.2
2883.4
2930.8
2896.8
2870.2
1672.9
1531.6
1595.3
1456.5
1456.4
1452.4
1476.0
1442.9
1375.6
1408.4
1355.9
1315.6
1240.8
------1232.9
1228.5
1212.1
1123.4
1064.6
1054.4
1078.0
1039.6
994.9
979.9
919.9
------908.0
895.3
809.2
794.6
730.9
542.3
Difference
-25.0
-14.9
3.2
-6.5
-11.2
40.9
-10.4
-24.9
57.7
-5.8
-9.3
5.4
43.2
137.6
-104.1
17.3
6.5
6.1
------14.6
28.9
-4.4
24.1
32.0
73.7
------57.1
0.3
-66.7
3.1
34.5
13.5
-57.8
-------3.3
-14.4
6.5
-------41.9
-128.5
-51.2
-66.4
-82.5
6.7
Assignment
CH2 asymmetric stretch
CH2 asymmetric stretch
C-H stretch
CH2 symmetric stretch
CH2 symmetric stretch
CH2 asymmetric stretch
CH3 asymmetric stretch
CH3 asymmetric stretch
CH2 asymmetric stretch
CH2 asymmetric stretch
CH2 symmetric stretch
CH3 symmetric stretch
N+-C stretch
CH2 scissor
CH2 twist
CH2 twist
CH3 twist
CH3 symmetric stretch
CH3 symmetric stretch
CH2 bend
CH2 scissor
CH3 umbrella
CH2 twist/CH3 umbrella
CH2 scissor/CH wag
C-H bend (out-of-plane)
C-H bend (out-of-plane)
CH wag
CH2 , CH3 twist
CH2 , CH3 rock
C-H wag (out-of-plane)
CH3 twist
CH2 twist
CH2 twist (out-of-plane)
CH2 twist
C-C-C stretch
CH2 wag
CH3 twist
CH2 twist
CH2 twist
CH2 twist
CH2 twist
H-C-H bend
CH2 twist
C-N+-C-C torison, CH2 wag
Supplemental Table 18: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-n-propyl-N-vinylmethyleneammonium (continued)
RHF/6-31G**
474.9
454.8
355.3
285.9
226.4
186.9
113.3
86.0
75.4
MM3(94)
524.1
506.4
363.7
301.0
229.4
217.7
128.1
80.9
45.8
Total of 49 Vibrations
Difference
-49.2
-51.6
-8.4
-15.1
-3.0
-30.8
-14.8
5.0
29.6
RMS: 45.0
Assignment
CH2 wag
CH2 wag
CH2 wag
CH2 wag
CH3 twist
N+ bend (out-of-plane)
CH=CH2 wag
C-N+-C-C torsion
C-N+-C-C torsion
Supplemental Table 19: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-isopropyl-N-vinylmethyleneammonium
RHF/6-31G**
3127.1
3107.0
3059.6
3023.6
3017.4
2985.7
2970.5
2962.1
2953.9
2949.7
2887.6
2882.0
1715.5
------1669.9
1478.2
1470.6
1461.9
1452.7
1448.4
1417.4
1411.0
------1395.5
1359.9
1343.7
1322.0
1275.2
1171.5
1130.3
1124.5
1101.8
1065.9
1018.5
967.3
929.9
------925.7
902.5
845.2
762.2
694.2
656.4
532.2
511.2
472.9
395.8
MM3(94)
3146.9
3118.7
3057.3
3027.5
3025.6
2948.7
2973.2
2970.8
2967.3
2978.7
2878.8
2880.3
1673.1
1573.1
1544.7
1484.8
1465.1
------1461.1
1458.4
1452.7
1442.1
1324.3
1409.3
1347.0
1250.0
------------1067.4
1236.0
1228.3
1129.9
1069.8
1026.8
1107.6
935.4
978.6
966.0
903.3
1091.4
859.3
757.2
723.0
575.2
538.9
481.9
410.6
Difference
-19.8
-11.7
2.2
-3.9
-8.2
37.0
-2.7
-8.7
-13.4
-28.9
8.8
1.7
42.4
------125.2
-6.6
5.5
-------8.4
-10.0
-35.3
-31.1
-------13.8
12.9
93.7
------------104.1
-105.7
-103.8
-28.1
-3.9
-8.3
-140.3
-5.5
-------40.3
-0.8
-246.2
-97.1
-63.0
-66.6
-43.0
-27.7
-9.0
-14.8
Assignment
CH2 asymmetric stretch
CH2 asymmetric stretch
C-H stretch
CH2 symmetric stretch
CH2 asymmetric stretch
CH3 asymmetric stretch
CH3 asymmetric stretch
CH3 asymmetric stretch
CH3 asymmetric stretch
CH3 asymmetric stretch
CH2 asymmetric stretch
CH3 symmetric stretch
N+-C stretch
C-H wag
CH wag, C-C stretch
CH2 scissor
CH3 twist
CH3 twist
CH3 twist
CH3 twist
CH2 scissor
CH3 bend (out-of-plane)
CH3 bend (out-of-plane)
CH3 umbrella
C-H wag
CH2 scissor
C-H wag
C-N+-C bend
CH3 twist
CH wag, CH2 bend (out-of-plane)
CCC bend
CH3 twist
CH2 wag
CH2 twist
CH wag, CH2 scissor
CH3 umbrella
CH3 twist
CH3 twist
CH2 wag
CH2 twist
CH2 twist
CCC bend
CH2 twist
CH2 wag
CH2 wag
CH2 wag
CH2 wag
Supplemental Table 19: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-isopropyl-N-vinylmethyleneammonium (continued)
RHF/6-31G**
337.2
284.9
266.5
233.6
209.4
101.3
61.3
Total 48 Vibrations
MM3(94)
334.0
254.2
289.5
245.2
222.5
104.5
50.5
Difference
3.2
30.7
-23.0
-11.6
-13.1
-3.2
10.8
RMS: 59.6
Assignment
C-C-N+-C torsion
CH3 rotation
CH3 twist
C-N+-C-C torsion
CH3 twist
H-C-C-H bend
CH3 bend
RHF/6-31G**
MM3(94)
MM2(91)
Relative Energy (kcal/mol)
0.6
0.4
0.2
0.0
0
30
60
90
120
150
180
Torsion Angle (Degrees), (=C-N+-C-H)
Supplemental Figure 1. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Profiles for N-methylpyridinium.
RHF/6-31G**
MM3(94)
MM2(91)
3.0
Relative Energy (kcal/mol)
2.5
2.0
1.5
1.0
0.5
0.0
0
30
60
90
120
150
180
Torsion Angle (Degrees), (=C-N+-C-C)
Supplemental Figure 2. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Profiles for N-n-propylpyridinium.
6
RHF/6-31G**
MM3(94)
MM2(91)
Relative Energy (kcal/mol)
5
4
3
2
1
0
0
30
60
90
120
150
180
Torsion Angle (Degrees), (=C-N+-C-C)
Supplemental Figure 3. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Profiles for N-isopropylpyridinium.
11
RHF/6-31G**
MM3(94)
MM2(91)
10
9
Relative Energy (kcal/mol)
8
7
6
5
4
3
2
1
0
0
30
60
90
120
150
180
Torsion Angle (Degrees), (=C-N+-C-C)
Supplemental Figure 4. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Profiles for s-trans-N-ethyl-N-vinylmethyleneammonium.
12
RHF/6-31G**
MM3(94)
MM2(94)
Relative Energy (kcal/mol)
10
8
6
4
2
0
0
30
60
90
120
150
180
Torsion Angle (Degrees), (=C-N+-C-C)
Supplemental Figure 5. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Profiles for s-trans-N-n-propyl-N-vinylmethyleneammonium.
12
RHF/6-31G**
MM3(94)
MM2(91)
Relative Energy (kcal/mol)
10
8
6
4
2
0
0
30
60
90
120
150
180
Torsion Angle (Degrees), (=C-N+-C-C)
Supplemental Figure 6. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Profiles for s-trans-N-isopropyl-N-vinylmethyleneammonium.
Supplemental Table 1. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
Pyridinium.
H8
H7
C3
H9
C2
C4
N+ 1 H11
C5
C6
H10
Bond
N+(1) - C(2)
N+(1) - C(6)
N+(1) - H(11)
RHF/6-31G**a
1.3638
1.3639
1.0121
MM2 (91)b
1.3520
1.3521
1.0128
RMS Diffc
Bond Angle
C(2) - N+(1) - C(6)
C(2) - N+(1) - H(11)
C(6) - N+(1) - H(11)
N+(1) - C(2) - C(3)
N+(1) - C(2) - H(7)
N+(1) - C(6) - C(5)
N+(1) - C(6) - H(12)
RHF/6-31G**d
123.139
118.428
118.428
119.682
116.761
119.682
116.761
MM2 (91)e
122.742
118.629
118.629
119.725
116.376
119.727
116.375
RMS Diff
________________
H12
Difference
-0.0118
-0.0118
0.0007
MM3(94)b
1.3546
1.3546
1.0140
0.0077
Difference
-0.397
0.201
0.201
0.043
-0.385
0.045
-0.386
0.212
Difference
-0.0092
-0.0093
0.0019
0.0065
MM3(94)e
124.048
117.976
117.976
119.443
116.091
118.443
116.091
Difference
0.909
-0.452
-0.452
-1.239
-0.670
-1.239
-0.670
0.659
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3 (94)
g
calculations of the pyridine and ethane structures.
b MM2 (91) and MM3 (94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3 (94) structures of pyridine and
ethane.
eMM2 (91) and MM3 (94) bond angles are given in degrees (°).
Supplemental Table 2. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
N-ethylpyridinium
H8
H7
C3
H9
N+ 1
RHF/6-31G**a
1.3641
1.3641
1.5037
RHF/6-31G**d
120.610
119.694
119.667
121.198
116.528
121.198
116.521
111.709
106.838
106.795
MM2(91)b
1.3650
1.3650
1.4989
MM2(91)e
120.391
119.616
119.490
120.743
117.294
120.746
117.274
111.426
107.618
107.538
RMS Diff
________________
C11
H14
H15
RMS Diffc
Bond Angle
C(2) - N+(1) - C(6)
C(2) - N+(1) - C(11)
C(6) - N+ (1) - C(11)
N+(1) - C(2) - C(3)
N+(1) - C(2) - H(7)
N+(1) - C(6) - C(5)
N+(1) - C(6) - H(15)
N+(1) - C(11) - C(12)
N+(1) - C(11) - H(13)
N+(1) - C(11) - H(14)
C12 H18
H13
C6
H10
Bond
N+(1) - C(2)
N+(1) - C(6)
N+(1) - C(11)
H16
C2
C4
C5
H17
Difference
0.0009
0.0009
-0.0048
MM3(94)b
1.3646
1.3645
1.5062
0.0060
Difference
-0.219
-0.078
-0.177
-0.455
0.766
-0.452
0.753
-0.283
0.780
0.743
0.439
Difference
0.0005
0.0004
0.0025
0.0043
MM3(94)e
120.106
119.944
119.944
120.679
115.584
120.679
115.584
110.976
106.988
106.988
Difference
-0.504
0.250
0.277
-0.519
-0.944
-0.519
-0.937
-0.733
0.150
0.193
0.469
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the pyridine and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of pyridine and
ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 3. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
N-n-propylpyridinium.
H8
H7
C3
H9
C2
C4
N+ 1
C5
H10
Bond
N+(1) - C(2)
N+(1) - C(6)
N+(1) - C(13)
H18
H17
RHF/6-31G**a
1.3640
1.3640
1.5028
RHF/6-31G**d
120.585
119.700
119.700
121.216
116.500
121.216
116.500
106.910
111.840
106.900
C6
C15
H21
C13
H20
H16
H11
MM2(91)b
1.3650
1.3650
1.4990
MM2(91)e
120.395
119.461
119.592
120.748
117.280
120.740
117.288
107.517
111.410
107.457
RMS Diff
________________
C14
H12
RMS Diffc
Bond Angle
C(2) - N+(1) - C(6)
C(2) - N+(1) - C(13)
C(6) - N+(1) - C(13)
N+(1) - C(2) - C(3)
N+(1) - C(2) - H(7)
N+(1) - C(6) - C(5)
N+(1) - C(6) - H(11)
N+(1) - C(13) - H(12)
N+(1) - C(13) - C(14)
N+(1) - C(13) - H(16)
H19
Difference
0.0010
0.0010
-0.0038
MM3(94)b
1.3644
1.3644
1.5123
0.0056
Difference
-0.190
-0.239
-0.108
-0.468
0.780
-0.476
0.788
0.607
-0.430
0.557
0.435
Difference
0.0004
0.0004
0.0095
0.0051
MM3(94)e
120.123
119.936
119.936
120.672
115.570
120.672
115.570
106.871
111.011
106.871
Difference
-0.462
0.236
0.236
-0.544
-0.930
-0.544
-0.930
-0.039
-0.829
-0.029
0.488
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the pyridine and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of pyridine and
ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 4. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
N-isopropylpyridinium
H8
H7
C3
H9
N+ 1
C6
H10
Bond
N+(1) - C(2)
N+(1) - C(6)
N+(1) - C(12)
RHF/6-31G**a
1.3631
1.3653
1.5217
RHF/6-31G**d
120.178
119.731
120.091
121.483
116.676
121.483
116.789
110.377
110.352
104.112
MM2(91)b
1.3666
1.3660
1.5060
MM2(91)e
120.120
120.175
119.705
120.836
117.770
120.894
117.573
111.471
111.439
107.023
RMS Diff
________________
C13 H18
C12
H21
H11 H
20
RMS Diffc
Bond Angle
C(2) - N+(1) - C(6)
C(2) - N+(1) - C(12)
C(6) - N+(1) - C(12)
N+(1) - C(2) - C(3)
N+(1) - C(2) - H(7)
N+(1) - C(6) - C(5)
N+(1) - C(6) - H(11)
N+(1) - C(12) - C(13)
N+(1) - C(12) - C(14)
N+(1) - C(12) - C(14)
H16
C2
C4
C5
H17
H15
C14
H19
Difference
0.0035
0.0007
-0.0157
MM3(94)b
1.3652
1.3662
1.5222
0.0069
Difference
-0.058
0.444
-0.386
-0.647
1.094
-0.589
0.784
1.094
1.087
2.911
0.958
Difference
0.0021
0.0009
0.0005
0.0042
MM3(94)e
119.710
120.038
120.251
120.873
115.912
120.907
115.817
110.633
110.633
105.585
Difference
-0.468
0.307
0.160
-0.610
-0.764
-0.576
-0.972
0.256
0.281
1.473
0.571
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the pyridine and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of pyridine and
ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 5. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
s-trans- N-vinylmethyleneammonium
H9
H10
H7
C4
C3
N+ 2
H8
Bond
C(1) - N+(2)
N+(2) - C(3)
N+(2) - H(7)
RHF/6-31G**a
1.3003
1.4506
1.0210
MM2(91)b
1.2892
1.4390
1.0130
RMS Diffc
Bond Angle
N+(2) - C(1) - H(5)
N+(2) - C(1) - H(6)
C(1) - N+(2) - C(3)
C(1) - N+(2) - H(7)
C(3) - N+(2) - H(7)
N+(2) - C(3) - C(4)
N+(2) - C(3) - H(8)
RHF/6-31G**d
119.988
119.699
126.019
117.853
116.128
120.840
114.206
MM2(91)e
118.943
117.269
126.305
117.126
116.569
121.153
116.695
RMS Diff
________________
C1
H5
H6
Difference
-0.0111
-0.0116
-0.0080
MM3(94)
1.2925
1.4450
1.0141
0.0082
Difference
-1.045
-2.430
0.286
-0.727
0.441
0.313
2.489
1.251
Difference
-0.0078
-0.0056
-0.0069
0.0062
MM3(94)
118.089
117.606
127.437
116.203
116.361
121.858
114.703
Difference
-1.899
-2.093
1.418
-1.650
0.233
1.018
0.497
1.250
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the pyridine and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of pyridine and
ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 6. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
s-trans- N-ethyl-N-vinylmethyleneammonium.
H16
H10
H6 H11
H7
C1
C2
C9
N+ 3
H8
Bond
C(2) - N+(3)
N+(3) - C(4)
N+(3) - C(5)
RHF/6-31G**a
1.4607
1.4995
1.3006
MM2(91)b
1.4661
1.5040
1.3015
RMS Diffc
Bond Angle
C(1) - C(2) - N+(3)
N+(3) - C(2) - H(8)
C(2) - N+(3) - C(4)
C(2) - N+(3) - C(5)
C(4) - N+(3) - C(5)
N+(3) - C(4) - C(9)
N+(3) - C(4) - H(10)
N+(3) - C(4) - H(11)
N+(3) - C(5) - H(12)
N+(3) - C(5) - H(13)
RHF/6-31G**d
124.771
112.916
120.379
119.470
120.145
111.840
106.385
111.187
120.363
120.098
MM2(91)e
124.360
115.858
120.038
121.277
118.568
111.923
108.359
107.605
118.802
119.494
RMS Diff
________________
H15
H14
C4
C5
H12
H13
Difference
0.0054
0.0045
0.0009
MM3(94)b
1.4596
1.5086
1.3011
0.0067
Difference
-0.411
2.942
-0.341
1.807
-1.577
0.083
1.974
0.776
-1.561
-0.604
1.354
Difference
-0.0011
0.0091
0.0005
0.0056
MM3(94)e
124.772
113.944
120.586
120.110
119.303
111.415
107.268
107.026
118.737
118.387
Difference
0.001
1.028
0.207
0.640
-0.842
-0.425
0.883
0.197
-1.626
-1.711
0.856
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the N-vinyl-2-ethylidenimine (s-trans) and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of N-vinyl-2ethylidenimine (s-trans) and ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 7. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
s-trans-N-n-propyl-N-vinylmethyleneammonium.
H15
H16
H12
H9
C4
C1
N+ 3
H10
Bond
C(2) - N+(3)
N+(3) - C(4)
N+(3) - C(7)
RHF/6-31G**a
1.4604
1.4987
1.3005
MM2(91)b
1.4662
1.5041
1.3015
RMS Diffc
Bond Angle
C(1) - C(2) - N+(3)
N+(3) - C(2) - H(10)
C(2) - N+(3) - C(4)
C(2) - N+(3) - C(7)
C(4) - N+(3) - C(7)
N+(3) - C(4) - C(5)
N+(3) - C(4) - H(11)
N+(3) - C(4) - H(12)
N+(3) - C(7) - H(18)
N+(3) - C(7) - H(19)
RHF/6-31G**d
124.807
112.911
120.471
119.420
120.102
112.011
106.451
106.917
120.054
120.393
MM2(91)e
124.363
115.854
120.037
121.297
118.552
111.966
108.249
107.502
119.474
118.805
RMS Diff
________________
H17
C5
H8 H11
C2
C6
H13
H14
C7
H18
H19
Difference
0.0058
0.0054
0.0010
MM3(94)b
1.4595
1.5147
1.3010
0.0063
Difference
-0.444
2.943
-0.434
1.877
-1.550
-0.045
1.798
0.585
-0.580
-1.588
1.283
Difference
-0.0009
0.0160
0.0005
0.0063
MM3(94)e
124.757
113.947
120.590
120.140
119.269
111.444
107.148
106.916
118.348
118.747
Difference
-0.050
1.036
0.119
0.720
-0.833
-0.567
0.697
-0.001
-1.706
-1.646
0.819
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the N-vinyl-2-ethylidenimine (s-trans) and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of N-vinyl-2ethylidenimine (s-trans) and ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 8. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
s-trans- N-isopropyl-N-vinylmethyleneammonium.
H19
H16
H6 H10
H17 C9
H15
C4
H14
C1
N+ 3
H18
H7
C11
C2
H8
Bond
C(2) - N+(3)
N+(3) - C(4)
N+(3) - C(5)
RHF/6-31G**a
1.4624
1.5186
1.3002
MM2(91)b
1.4687
1.5074
1.2975
RMS Diffc
Bond Angle
C(1) - C(2) - N+(3)
N+(3) - C(2) - H(8)
C(2) - N+(3) - C(4)
C(2) - N+(3) - C(5)
C(4) - N+(3) - C(5)
N+(3) - C(4) - C(9)
N+(3) - C(4) - C(10)
N+(3) - C(4) - H(11)
N+(3) - C(5) - H(12)
N+(3) - C(5) - H(13)
RHF/6-31G**d
125.651
112.642
119.713
118.430
121.838
108.960
112.196
103.910
120.125
120.658
MM2(91)e
123.563
115.680
119.535
121.057
119.394
110.952
112.872
106.480
118.527
119.545
RMS Diff
________________
C5
H12
H13
Difference
0.0063
-0.0112
-0.0027
MM3(94)b
1.4631
1.5232
1.2997
0.0078
Difference
-2.088
3.038
-0.178
2.627
-2.444
1.992
0.676
2.570
-1.598
-1.113
1.856
Difference
0.0007
0.0046
-0.0005
0.0060
MM3(94)e
124.494
113.852
120.387
119.539
120.074
110.172
111.722
105.401
118.487
118.743
Difference
-1.157
1.210
0.674
1.109
-1.764
1.212
-0.474
1.491
-1.638
-1.915
1.220
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the N-vinyl-2-ethylidenimine (s-trans) and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of N-vinyl-2ethylidenimine (s-trans) and ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 9. RHF/6-31G**, MM2(91), and MM3(94) Structural Results for
s-trans-N-n-butyl-N-vinylmethyleneammonium.
H20
H19
H18
H15
H10 H14
H9
C1
C2
RHF/6-31G**a
1.4602
1.3004
1.4992
RHF/6-31G**d
124.798
112.920
119.414
120.472
120.108
120.401
120.040
112.003
106.393
106.864
MM2(91)b
1.4663
1.3015
1.5041
MM2(91)e
124.363
115.854
121.298
120.042
118.545
118.805
119.474
111.935
108.227
107.489
RMS Diff
________________
H17
H16
N+ 3
RMS Diffc
Bond Angle
C(1) - C(2) - N+(3)
N+(3) - C(2) - H(11)
C(2) - N+(3) - C(4)
C(2) - N+(3) - C(5)
C(4) - N+(3) - C(5)
N+(3) - C(4) - H(12)
N+(3) - C(4) - H(13)
N+(3) - C(5) - C(6)
N+(3) - C(5) - H(14)
N+(3) - C(5) - H(15)
C8 H
22
H21
C6
C5
H11
Bond
C(2) - N+(3)
N+(3) - C(4)
N+(3) - C(5)
C7
C4
H13
H12
Difference
0.0061
0.0011
0.0049
MM3(94)b
1.4595
1.3010
1.5147
0.0062
Difference
-0.435
2.934
1.884
-0.430
-1.563
-1.596
-0.566
-0.068
1.834
0.625
1.242
Difference
-0.0007
0.0006
0.0155
0.0060
MM3(94)e
124.754
113.948
120.145
120.583
119.270
118.747
118.346
111.414
107.146
106.886
Difference
-0.044
1.028
0.731
0.111
-0.838
-1.654
-1.694
-0.589
0.753
0.022
0.794
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to r bond lengths based on MM3(94)
g
calculations of the N-vinyl-2-ethylidenimine (s-trans) and ethane structures.
b MM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as r bond lengths.
g
cThe RMS difference in the calculated bond lengths reported in this Table represent the RMS difference of all the
bonds and not just the RMS of those reported.
d RHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of N-vinyl-2ethylidenimine (s-trans) and ethane.
eMM2(91) and MM3(94) bond angles are given in degrees (°).
Supplemental Table 10: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for Pyridinium.
RHF/6-31G**
3432.4
3079.0
3077.7
3067.0
3065.6
3048.0
------1635.8
1631.6
1544.1
1482.8
1378.4
1291.7
1197.6
1185.0
1112.6
1052.1
1044.4
1041.5
1016.6
1012.6
1010.5
980.4
883.4
842.0
737.8
652.5
621.2
596.8
395.4
383.1
MM3(94)
3426.2
3081.3
3079.9
3068.9
3065.0
3056.1
1696.7
1638.5
1656.1
1509.8
1455.4
1381.7
1223.8
1203.3
1150.3
------1147.7
978.9
995.8
1092.0
935.5
1026.7
911.7
818.6
851.5
750.4
632.4
581.5
584.5
397.4
425.6
Total of 29 Vibrations
Difference
6.2
-2.3
-2.2
-1.9
0.6
-8.1
-------2.7
-24.5
34.3
27.4
-3.3
67.9
-5.7
34.7
-------95.6
65.5
45.7
-75.4
77.1
-16.2
68.7
64.8
-9.5
-12.6
20.1
39.7
12.3
-2.0
-42.5
RMS: 41.1
Assignment
N+-H stretching
CH2 sym/sym stretch
CH2 sym/asym stretch
CH2 asym/sym stretch
CH2 asym/asym stretch
CH2 sym str + N+-H str
Csp2 -Csp2 asym stretch
N+-Csp2 asym stretch
Csp2 -Csp2 asym stretch
CH2 asym wag
Csp2 -Csp2 asym stretch
CH2 sym wag
CH2 asym wag + N+-H wag
CH2 asym wag
CH2 sym wag
Csp2 -Csp2 stretch
CH2 out-of-plane wag
N+-Csp2 symm stretch
Csp2 -Csp2 asym stretch
CH2 out-of-plane wag
Skeletal bending
CH2 out-of-plane wag
Ring Breathing
CH2 out-of-plane wag
CH2 out-of-plane wag
CH2 out-of-plane bending
CH2 out-of-plane bending
Skeletal bending
Skeletal bending
Ring twisting
Ring deformation
Supplemental Table 11: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for N-methylpyridinium
RHF/6-31G**
3077.6
3075.1
3065.2
3062.7
3048.5
3018.1
3004.9
2916.6
1649.0
------1602.6
1501.7
1491.0
1455.7
1448.6
1428.3
1361.6
1222.1
------1203.3
1177.5
1134.7
1127.9
1107.5
1049.1
1042.5
1021.2
1014.9
1008.2
991.3
880.0
779.6
766.4
664.4
636.6
514.4
438.8
395.6
373.9
193.6
18.7
-------
MM3(94)
3079.2
3075.2
3067.3
3062.0
3055.6
2981.8
2991.6
2869.5
1674.8
1676.6
1617.2
1510.9
1454.0
1385.8
1419.6
1420.9
1299.0
1226.1
1178.6
1177.5
1163.4
------1100.9
------1112.8
980.6
1044.4
1116.1
931.4
996.2
846.1
747.3
771.9
664.8
581.1
509.2
447.8
374.5
406.1
198.1
-------15.9
Total of 36 Vibrations
Difference
-1.6
-0.1
-2.1
0.7
-7.1
36.3
13.3
47.1
-25.8
-------14.6
-9.2
37.0
69.9
29.0
7.4
62.6
-4.0
------25.8
14.1
------27.0
-------63.7
61.9
-23.2
-101.2
76.8
-4.9
33.9
32.3
-5.5
-0.4
55.5
5.2
-9.0
21.1
-32.2
-4.5
------------RMS: 36.9
Assignment
C-H sym/sym stretch
C-H sym/asym stretch
C-H asym/sym stretch
C-H asym/asym stretch
C-H stretch
CH3 asym stretch
CH3 asym stretch
CH3 sym stretch
Csp2 =Csp2 sym stretch
Csp2 =Csp2 + N+-Csp2 asym str
Csp2 =Csp2 + N+-Csp2 asym str
Csp2 =Csp2 + N+-Csp2 sym str
Csp2 =Csp2 + N+-Csp2 asym str
CH3 asym bend
CH3 asym bend (C-H wagging)
CH3 sym bend
C-H sym wag (in-plane)
C-H asym + CH3 wag (in-plane)
CH3 wag + CH out-of-plane bend
C-H asym wag (in-plane)
CH3 stretch + skeletal bend
C-H wag + CH3 rocking
CH3 wagging (out-of-plane)
Csp2 =Csp2 asym stretch
C-H asym wag (out-of-plane)
Csp2 =Csp2-Csp2 bending
Csp2 =Csp2 + N+-Csp2 asym str
C-H asym wag (out-of-plane)
Ring Breathing
C-H sym wag (out-of-plane)
C-H asym wag (out-of-plane)
C-H sym wag (out-of-plane)
Csp2 =Csp2-Csp2 bending
Ring out-of-plane deformation
Ring bending (in-plane)
Ring bending (in-plane)
Ring bending (out-of-plane)
Ring twisting
CH3 in-plane wag
CH3 out-of-plane wag
CH3 torsion
CH3 torsion
Supplemental Table 12: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for N-ethylpyridinium.
RHF/6-31G**
3076.3
3073.9
3064.4
3061.8
3048.0
2992.3
2961.6
2950.6
2938.6
2883.0
1647.4
1603.4
1503.9
1485.3
1471.5
1454.2
------1452.4
1404.7
1363.9
1355.8
1283.9
1202.0
1200.9
1161.8
1141.6
1105.4
1081.6
1048.5
1042.7
------1038.8
1015.1
1008.3
993.1
935.3
880.8
787.1
773.7
739.8
672.8
636.6
536.0
470.4
396.4
379.2
310.2
217.9
129.7
50.7
MM3(94)
3078.6
3076.3
3067.6
3062.2
3055.7
2948.1
2969.9
2970.2
2892.3
2874.0
1678.7
1619.1
1485.7
1676.6
1556.5
1433.0
1459.9
1451.6
1452.6
1353.2
1370.6
------1234.1
1176.7
1190.7
1221.3
1062.5
1026.0
1154.5
------1036.6
1026.0
1116.1
931.0
1000.5
983.0
846.6
787.8
838.0
754.4
665.0
581.2
540.3
459.7
375.3
406.2
329.1
218.8
135.2
58.5
Total of 46 Vibrations
Difference
-2.3
-2.4
-3.2
-0.4
-7.7
44.2
-8.3
-19.6
46.3
9.0
-31.3
-15.7
18.2
-191.3
-85.0
21.2
------0.8
-47.9
10.7
-14.8
-------32.1
24.2
-28.9
-79.7
42.9
55.6
-106.0
------------12.8
-101.0
77.3
-7.4
-47.7
34.2
-0.7
-64.3
-14.6
7.8
55.4
-4.3
10.7
21.1
-27.0
-18.9
-0.9
-5.5
-7.8
RMS: 48.3
Assignment
C-H sym/sym stretch
C-H sym/asym stretch
C-H asym/sym stretch
C-H asym/asym stretch
C-H stretch
CH2 asym stretch
CH3 asym stretch
CH3 asym stretch
CH2 sym stretch
CH3 sym stretch
Csp2 =Csp2 stretch
Csp2 =Csp2 + N+-Csp2 asym str
Csp2 =Csp2 + N+-Csp2 sym str
C-H wag (in-plane)
CH2 + CH3 asym bend
CH2 + CH3 asym bend
CH3 asym bend
CH3 asym bend
CH3 sym bend
C-H sym wag (in-plane)
CH3 + CH2 wag
C-H wag (in-plane) + CH2 wag
C-H wag (in-plane)
C-H asym wag (in-plane)
N+-Csp3 stretch
C-H wag + CH2 wag (in-plane)
Csp2 =Csp2 stretch
CH3 rock
C-H wag (out-of-plane)
Csp2 =Csp2-Csp2(N+) asym bend
C-H asym wag (out-of-plane)
Csp2 =Csp2 + N+-Csp2 sym str
C-H asym wag (out-of-plane)
Ring breathing
C-H asym wag (out-of-plane)
Ring breathing + CH3 rock
C-H asym wag (out-of-plane)
C-H sym wag (out-of-plane)
CH2 + CH3 wag
Ring bending (Csp2 =Csp2-Csp2)
Ring out-of-plane deformation
Ring bending
Ring bending
Ring bending (Csp2 -N+=Csp2)
Ring twisting
Ethyl in-plane bending
Ethyl bending + ring bending
CH3 torsion
Ethyl bending
Ethyl torsion
Supplemental Table 13: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for N-n-propylpyridinium
RHF/6-31G**
3076.8
3074.3
3064.6
3062.0
3047.8
2985.0
2956.3
2938.4
2932.5
2909.6
2876.6
2875.1
1647.7
1603.4
1503.5
1485.0
1476.2
1463.0
1462.9
1455.3
------1403.7
1379.8
1363.6
1305.6
1299.6
1261.3
1200.9
1196.7
1160.0
1145.3
1104.7
1098.9
1048.1
1043.8
1042.9
1015.0
1008.3
994.3
993.7
881.0
876.6
860.3
794.2
------771.6
725.3
673.2
636.7
578.0
MM3(94)
3078.7
3076.5
3067.6
3062.3
3055.7
2949.4
2968.6
2970.2
2891.3
2924.9
2867.6
2881.3
1679.5
1619.2
1487.8
1676.6
1458.3
1456.9
1453.8
1439.1
1452.9
1395.4
1569.1
1357.3
1351.6
1224.6
1240.2
1175.5
1221.9
1185.2
1033.7
------1060.1
1155.0
1058.8
981.2
1116.2
931.7
1015.4
993.0
846.7
899.7
902.6
762.8
803.1
665.2
787.0
------581.2
568.4
Difference
-1.9
-2.2
-3.0
-0.3
-7.8
35.6
-12.3
-31.8
41.2
-15.3
9.0
-6.2
-31.8
-15.8
15.7
-191.6
17.9
6.0
9.1
16.2
------8.3
-189.3
6.3
-46.0
75.0
21.1
25.4
-25.2
-25.2
111.6
------38.8
-106.9
-15.0
61.7
-101.2
76.6
-21.1
0.7
34.3
-23.1
-42.3
31.4
------106.4
-61.7
------55.5
9.6
Assignment
C-H sym/sym stretch
C-H sym/asym stretch
C-H asym/sym stretch
C-H asym/asym stretch
C-H stretch
CH2 asym stretch
CH3 asym stretch
CH3 asym stretch
CH2 sym stretch
CH2 asym stretch
CH2 sym stretch
CH3 sym stretch
Csp2 =Csp2 stretch
Csp2 =Csp2 + N+-Csp2 asym str
Csp2 =Csp2 + N+-Csp2 sym str
Csp2 =Csp2 + N+-Csp2 asym str
CH2 + CH3 asym bend
CH3 asym bend
CH2 + CH3 asym bend
CH2 + CH3 asym bend
CH2 + CH3 asym bend
CH3 wag
CH2 asym wag
C-H sym wag (in-plane)
CH2 asym wag
CH2 sym wag
CH2 asym wag
C-H wag (in-plane)
C-H asym wag (in-plane)
N+-Csp3 stretch
C-H asym wag (in-plane)
C-H sym wag (in-plane)
CH2 -CH2 stretch
C-H asym bend (out-of-plane)
C-H sym wag (in-plane)
Ring bending (Csp2 =Csp2-Csp2)
C-H wag (out-of-plane)
Ring breathing
C-H wag (out-of-plane)
Csp3 -Csp3-Csp3 bending
C-H sym wag (out-of-plane)
Csp3 -Csp3-Csp3 bending
CH2 + CH3 bending
Ring deformation (out-of-plane)
Ring deformation (in-plane)
C-H sym wag (out-of-plane)
CH2 twist
N+ out-of-plane bend
Ring deformation (in-plane)
Ring deformation (in-plane)
Supplemental Table 13: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for N-n-propylpyridinium (continued)
RHF/6-31G**
468.8
396.6
372.5
301.8
266.3
225.5
99.5
83.7
49.0
MM3(94)
461.5
375.0
397.1
300.3
295.3
227.5
106.2
50.3
57.1
Total of 55 Vibrations
Difference
7.3
21.6
-24.6
1.5
-29.0
-2.0
-6.8
33.4
-8.1
RMS: 54.2
Assignment
Ring deformation (out-of-plane)
Ring twisting
CH2 wag
CH3 wag
Propyl wag
CH3 twisting
CH2 -CH2 bending
CH2 -CH2 torsion
Propyl torsion
Supplemental Table 14: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for N-isopropylpyridinium
RHF/6-31G**
3090.8
3078.7
3066.1
3063.0
3047.8
2965.5
2962.2
2959.5
2950.4
2941.7
2885.5
2882.2
1645.7
1603.4
------1500.2
1485.9
1466.8
1462.9
1454.0
1445.9
1415.4
1397.6
1380.7
1338.5
1326.9
1203.7
1201.7
1175.7
1143.6
1122.5
1108.8
1095.0
1048.4
1046.7
1039.3
1016.1
1006.6
994.8
926.1
918.6
879.7
860.9
790.0
712.0
675.4
635.7
547.1
506.0
453.3
MM3(94)
3088.2
3079.5
3068.7
3062.7
3055.9
2977.0
2969.6
2968.1
2976.2
2930.7
2879.0
2880.2
1675.8
1628.8
1680.9
1496.6
1553.4
1471.6
1469.4
1459.3
1457.0
1409.0
1443.8
1431.2
1287.0
1343.2
1184.7
1227.3
1091.2
1211.3
1092.1
1037.2
1032.5
1160.0
974.1
930.1
1116.3
------1009.5
940.7
971.1
847.6
870.1
782.0
737.6
665.9
587.8
563.3
481.7
466.3
Difference
2.6
-0.8
-2.6
0.3
-8.1
-11.5
-7.4
-8.6
-25.8
11.0
6.5
2.1
-30.1
-25.4
------3.6
-67.5
-4.8
-6.5
-5.3
-11.1
6.4
-46.2
-50.5
51.5
-16.3
19.0
-25.6
84.5
-67.7
30.4
71.6
62.5
-111.6
72.6
109.2
-100.2
-------14.7
-14.6
-52.5
32.1
-9.2
8.0
-25.6
9.5
47.9
-16.2
24.3
-13.0
Assignment
C-H sym/sym stretch
C-H sym/asym stretch
C-H asym/sym stretch
C-H asym/asym stretch
C-H stretch
CH3 sym/asym stretch
CH3 sym/asym stretch
CH3 asym/asym stretch
CH3 asym/asym stretch
C-H isopropyl stretch
CH3 sym/sym stretch
CH3 asym/sym stretch
Csp2 =Csp2 stretch
Csp2 =Csp2 + N+-Csp2 asym str
C-H wag (in-plane)
Csp2 =Csp2 + N+-Csp2 sym str
Csp2 =Csp2 + N+-Csp2 asym str
CH3 sym/asym bending
CH3 sym/asym bending
CH3 asym/asym bending
CH3 asym/asym bending
CH3 sym/sym bending
CH3 asym/sym bending
C-H wag (in-plane)
C-H isopropyl wag
C-H isopropyl wag
C-H asym wag (in-plane)
C-H asym wag (in-plane)
C-H asym wag (in-plane)
N+-Csp2 stretch
CH3 asym stretch
Ring bending (Csp2 =Csp2-Csp2)
Ring bending (Csp2 =Csp2-Csp2)
C-H wag (out-of-plane)
Ring bending (Csp2 =Csp2-Csp2)
Ring deformation (in-plane)
C-H wag (out-of-plane)
Ring breathing
C-H wag (out-of-plane)
CH3 asym wag
CH3 asym wag
C-H wag (out-of-plane)
CH3 sym wag
C-H wag (out-of-plane)
Ring deformation (in-plane)
C-H wag (out-of-plane)
Ring deformation (in-plane)
Isopropyl deformation
Ring deformation (out-of-plane)
H3C-CH-CH3 bending
Supplemental Table 14: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for N-isopropylpyridinium (continued)
RHF/6-31G**
398.6
322.0
297.2
254.0
226.1
222.8
121.1
43.6
MM3(94)
379.9
344.7
302.7
237.1
255.5
233.5
125.6
55.7
Total of 56 Vibrations
Difference
18.7
-22.7
-5.5
16.9
-29.4
-10.7
-4.5
-12.1
RMS: 39.7
Assignment
Ring twisting
CH3 asym twisting
CH3 sym twisting
CH3 torsion (sym)
Isopropyl rocking
CH3 torsion (asym)
Isopropyl wag
Isopropyl torsion
Supplemental Table 15: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-vinylmethyleneammonium
RHF/6-31G**
3387.5
3113.2
3096.2
3068.0
3002.8
3001.8
1724.9
1663.4
1487.7
1409.4
1389.1
1302.7
1213.5
1137.2
1039.7
1028.3
1021.0
940.5
848.4
747.4
527.8
510.5
314.6
129.6
MM3(94)
3422.4
3135.0
3112.7
3069.4
3021.8
3014.1
1747.6
1589.1
1426.7
1413.5
1241.2
1195.4
1147.9
1134.6
997.1
1071.2
1051.5
994.0
864.5
812.4
500.1
581.3
352.8
139.2
Total of 24 Vibrations
Difference
-34.9
-21.8
-16.5
-1.4
-19.0
-12.3
-22.7
74.3
61.0
-4.1
147.9
107.3
65.6
2.6
42.6
-42.9
-30.5
-53.5
-16.1
-65.0
27.7
-70.8
-38.3
-9.6
RMS: 53.7
Assignment
N+-H stretching
CH2 asym stretch
CH2 asym stretch
C-H stretch
CH2 sym stretch
CH2 sym stretch
N+-Csp2 stretch
Csp2 -Csp2 stretch
CH2 scissor
N+-H wag
CH2 wag
C-H wag
CH2 wag
CH2 out-of-plane wag
CH2 in-plane wag
CH2 out-of-plane wag
CH2 out-of-plane wag
N+-H + CH 2 out-of-plane wag
CH2 in-plane wag
Vinyl wag
N+-Csp2=Csp2 bend
CH2 twist
Csp2 -N+-Csp2 bend
Skeletal torsion
Supplemental Table 16: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-methyl-N-vinylmethyleneammonium
RHF/6-31G**
3115.3
3105.2
3065.0
3023.3
3020.4
3010.7
3007.6
2919.4
1720.4
1669.1
1487.8
1446.7
1444.1
1427.8
1401.3
1344.0
------1300.4
1137.5
MM3(94)
3137.2
3118.1
3059.5
3027.2
2990.2
2985.0
3017.9
2870.5
1669.6
1553.5
1410.1
1437.2
1440.0
------1471.9
1294.9
1285.7
1234.0
1245.5
Difference
-21.9
-12.9
5.5
-3.9
30.2
25.7
-10.3
48.9
50.8
115.6
77.7
9.5
4.1
-------70.6
49.1
------66.4
-108.0
1123.1
1142.8
-19.7
1118.4
1065.7
1023.5
961.6
1099.4
1047.7
1124.4
1069.4
19.0
18.0
-100.9
-107.8
932.3
------759.8
753.6
631.0
534.7
473.2
393.0
308.2
216.5
107.3
905.0
968.4
723.2
783.4
------539.8
501.4
492.2
325.1
256.0
96.9
Total of 31 Vibrations
27.3
------36.6
-29.8
-------5.1
-28.2
-99.2
-16.9
-39.5
10.4
RMS: 53.5
Assignment
CH2 asym stretch
CH2 asym stretch
C-H stretch
CH2 sym + CH3 asym stretch
CH2 sym str + CH3 asym str
CH3 asym stretch
CH2 sym stretch
CH3 sym stretch
N+=Csp2 stretch
Csp2 =Csp2 stretch
CH2 scissor + CH3 asym bend
CH2 asym bend + CH2 scissor
CH3 asym bend
CH3 sym bend
CH2 scissor
C-H wag (in-plane) + N+-CH3 str
CH2 scissor
C-H wag (in-plane) + N+-CH3 str
CH3 rock + CH2 wag (out-ofplane)
CH2 wag (out-of-plane) + CH3
rock
CH3 wag
CH2 asym wag (in-plane)
CH2 wag (out-of-plane)
C-H wag (out-of-plane) + CH2
twist
CH2 sym wag (in-plane)
CH2 twist
CH2 sym twist
N+-Csp2 + N+-CH3 stretch
CH2 twist
Csp2 =Csp2-N+ bend
Csp2 -N+=Csp2 bend
N+ out-of-plane bend
Csp2 =Csp2-N+ bend
CH3 torsion
Skeletal torsion
Supplemental Table 17: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-ethyl-N-vinylmethyleneammonium
RHF/6-31G**
3112.1
3105.9
3061.5
3022.7
3006.9
3002.2
2973.4
2959.6
2947.9
2891.2
1716.1
1669.0
1491.8
1462.8
1458.3
1452.0
1405.7
1404.0
1361.6
1342.6
1305.3
1248.9
1137.9
1127.7
1085.0
1067.3
1021.3
967.0
MM3(94)
3137.2
3121.2
3058.0
3029.3
3017.8
2954.6
2977.2
2969.3
2897.5
2877.6
1672.9
1586.9
1468.7
1526.2
1456.1
1460.2
1442.5
1387.1
1314.1
1370.3
1240.0
1210.8
1065.0
1232.4
1042.9
1027.2
1123.4
1077.5
961.1
890.4
786.7
762.1
709.9
655.9
535.4
472.4
465.1
330.1
241.0
200.0
119.8
87.7
996.3
897.6
854.9
942.2
776.5
728.8
549.1
528.4
494.1
352.8
272.1
210.5
134.4
82.3
Total of 42 Vibrations
Difference
-25.1
-15.3
3.5
-6.7
-10.9
47.6
-3.8
-9.7
50.4
13.7
43.2
82.1
23.1
-63.4
2.2
-8.2
-36.8
16.9
47.5
-27.7
65.3
38.1
72.9
-104.7
42.0
40.1
-102.1
-110.5
-35.2
-7.2
-68.2
-180.1
-66.6
-72.9
-13.7
-56.0
-29.0
-22.7
-31.1
-10.5
-14.6
5.4
RMS: 54.8
Assignment
CH2 asym stretch
CH2 asym stretch
C-H stretch
CH2 sym stretch
CH2 sym str + Csp3 -H asym str
Csp3 -H asym str
CH3 asym stretch
CH3 asym stretch
Csp3 -H sym stretch
CH3 sym stretch
N+-Csp2 + Csp2=Csp2 stretch
Csp2 =Csp2 + N+-Csp2 stretch
CH2 scissor
CH3 asym bend + CH2 scissor
CH3 asym bend + CH2 scissor
CH3 asym bend
CH3 sym bend + CH2 scissor
CH3 sym bend + CH2 scissor
CH2 (ethyl) asym bend
C-H wag + CH2 asym bend
C-H wag + CH2 (ethyl) wag
CH2 (ethyl) + CH2 wag (in-plane)
CH3 rock
CH2 wag (out-of-plane)
CH3 wag
CH2 asym wag (in-plane)
CH2 wag (out-of-plane)
C-H wag (out-of-plane) + CH2
twist
Csp3 -Csp3 stretch
CH2 sym wag (in-plane)
Ethyl wag
CH2 twisting
Csp2 -N+ str + CH3 rock
CH2 twist
Csp2 =N+-Csp2 bend
N+ out-of-plane bend
CH2 wag (in-plane)
Csp2 =Csp2-N+ bend
Csp3 -Csp3-N+ bend
CH3 torsion
Ethyl torsion
Skeletal torsion
Supplemental Table 18: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-n-propyl-N-vinylmethyleneammonium
RHF/6-31G**
3112.4
3106.2
3061.3
3022.7
3006.7
2997.0
2958.2
2945.3
2941.1
2925.0
2887.5
2875.6
1716.1
1669.2
1491.2
1473.7
1463.0
1458.5
------1457.5
1404.5
1404.0
1380.0
1347.6
1314.5
1297.2
1290.0
1228.8
1145.4
1126.5
1099.1
1067.9
1020.2
------991.6
965.5
926.4
878.8
866.1
766.8
758.0
728.2
648.4
549.0
MM3(94)
3137.4
3121.1
3058.1
3029.2
3017.9
2956.1
2968.6
2970.2
2883.4
2930.8
2896.8
2870.2
1672.9
1531.6
1595.3
1456.5
1456.4
1452.4
1476.0
1442.9
1375.6
1408.4
1355.9
1315.6
1240.8
------1232.9
1228.5
1212.1
1123.4
1064.6
1054.4
1078.0
1039.6
994.9
979.9
919.9
------908.0
895.3
809.2
794.6
730.9
542.3
Difference
-25.0
-14.9
3.2
-6.5
-11.2
40.9
-10.4
-24.9
57.7
-5.8
-9.3
5.4
43.2
137.6
-104.1
17.3
6.5
6.1
------14.6
28.9
-4.4
24.1
32.0
73.7
------57.1
0.3
-66.7
3.1
34.5
13.5
-57.8
-------3.3
-14.4
6.5
-------41.9
-128.5
-51.2
-66.4
-82.5
6.7
Assignment
CH2 asymmetric stretch
CH2 asymmetric stretch
C-H stretch
CH2 symmetric stretch
CH2 symmetric stretch
CH2 asymmetric stretch
CH3 asymmetric stretch
CH3 asymmetric stretch
CH2 asymmetric stretch
CH2 asymmetric stretch
CH2 symmetric stretch
CH3 symmetric stretch
N+-C stretch
CH2 scissor
CH2 twist
CH2 twist
CH3 twist
CH3 symmetric stretch
CH3 symmetric stretch
CH2 bend
CH2 scissor
CH3 umbrella
CH2 twist/CH3 umbrella
CH2 scissor/CH wag
C-H bend (out-of-plane)
C-H bend (out-of-plane)
CH wag
CH2 , CH3 twist
CH2 , CH3 rock
C-H wag (out-of-plane)
CH3 twist
CH2 twist
CH2 twist (out-of-plane)
CH2 twist
C-C-C stretch
CH2 wag
CH3 twist
CH2 twist
CH2 twist
CH2 twist
CH2 twist
H-C-H bend
CH2 twist
C-N+-C-C torison, CH2 wag
Supplemental Table 18: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-n-propyl-N-vinylmethyleneammonium (continued)
RHF/6-31G**
474.9
454.8
355.3
285.9
226.4
186.9
113.3
86.0
75.4
MM3(94)
524.1
506.4
363.7
301.0
229.4
217.7
128.1
80.9
45.8
Total of 49 Vibrations
Difference
-49.2
-51.6
-8.4
-15.1
-3.0
-30.8
-14.8
5.0
29.6
RMS: 45.0
Assignment
CH2 wag
CH2 wag
CH2 wag
CH2 wag
CH3 twist
N+ bend (out-of-plane)
CH=CH2 wag
C-N+-C-C torsion
C-N+-C-C torsion
Supplemental Table 19: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-isopropyl-N-vinylmethyleneammonium
RHF/6-31G**
3127.1
3107.0
3059.6
3023.6
3017.4
2985.7
2970.5
2962.1
2953.9
2949.7
2887.6
2882.0
1715.5
------1669.9
1478.2
1470.6
1461.9
1452.7
1448.4
1417.4
1411.0
------1395.5
1359.9
1343.7
1322.0
1275.2
1171.5
1130.3
1124.5
1101.8
1065.9
1018.5
967.3
929.9
------925.7
902.5
845.2
762.2
694.2
656.4
532.2
511.2
472.9
395.8
MM3(94)
3146.9
3118.7
3057.3
3027.5
3025.6
2948.7
2973.2
2970.8
2967.3
2978.7
2878.8
2880.3
1673.1
1573.1
1544.7
1484.8
1465.1
------1461.1
1458.4
1452.7
1442.1
1324.3
1409.3
1347.0
1250.0
------------1067.4
1236.0
1228.3
1129.9
1069.8
1026.8
1107.6
935.4
978.6
966.0
903.3
1091.4
859.3
757.2
723.0
575.2
538.9
481.9
410.6
Difference
-19.8
-11.7
2.2
-3.9
-8.2
37.0
-2.7
-8.7
-13.4
-28.9
8.8
1.7
42.4
------125.2
-6.6
5.5
-------8.4
-10.0
-35.3
-31.1
-------13.8
12.9
93.7
------------104.1
-105.7
-103.8
-28.1
-3.9
-8.3
-140.3
-5.5
-------40.3
-0.8
-246.2
-97.1
-63.0
-66.6
-43.0
-27.7
-9.0
-14.8
Assignment
CH2 asymmetric stretch
CH2 asymmetric stretch
C-H stretch
CH2 symmetric stretch
CH2 asymmetric stretch
CH3 asymmetric stretch
CH3 asymmetric stretch
CH3 asymmetric stretch
CH3 asymmetric stretch
CH3 asymmetric stretch
CH2 asymmetric stretch
CH3 symmetric stretch
N+-C stretch
C-H wag
CH wag, C-C stretch
CH2 scissor
CH3 twist
CH3 twist
CH3 twist
CH3 twist
CH2 scissor
CH3 bend (out-of-plane)
CH3 bend (out-of-plane)
CH3 umbrella
C-H wag
CH2 scissor
C-H wag
C-N+-C bend
CH3 twist
CH wag, CH2 bend (out-of-plane)
CCC bend
CH3 twist
CH2 wag
CH2 twist
CH wag, CH2 scissor
CH3 umbrella
CH3 twist
CH3 twist
CH2 wag
CH2 twist
CH2 twist
CCC bend
CH2 twist
CH2 wag
CH2 wag
CH2 wag
CH2 wag
Supplemental Table 19: RHF/6-31G** and MM3(94) Vibrational Frequency Results
for s-trans-N-isopropyl-N-vinylmethyleneammonium (continued)
RHF/6-31G**
337.2
284.9
266.5
233.6
209.4
101.3
61.3
Total 48 Vibrations
MM3(94)
334.0
254.2
289.5
245.2
222.5
104.5
50.5
Difference
3.2
30.7
-23.0
-11.6
-13.1
-3.2
10.8
RMS: 59.6
Assignment
C-C-N+-C torsion
CH3 rotation
CH3 twist
C-N+-C-C torsion
CH3 twist
H-C-C-H bend
CH3 bend