180 150
120 90
60 30
0 0.0 0.2 0.4 0.6
0.8 RHF/6-31G**
MM3(94) MM2(91)
Torsion Angle (Degrees), (=C-N+-C-H)
180 150
120 90
60 30
0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
MM3(94) MM2(91)
Torsion Angle (Degrees), (=C-N+-C-C)
Relative Energy (kcal/mol)
Supplemental Figure 2. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
180 150
120 90
60 30
0 0 1 2 3 4 5
RHF/6-31G** MM3(94) MM2(91)
Torsion Angle (Degrees), (=C-N+-C-C)
180 150
120 90
60 30
0 0 1 2 3 4 5 6 7 8 9
10 RHF/6-31G**MM3(94)
MM2(91)
Torsion Angle (Degrees), (=C-N+-C-C)
Relative Energy (kcal/mol)
Supplemental Figure 4. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
180 150
120 90
60 30
0 0 2 4 6 8 10
RHF/6-31G** MM3(94) MM2(94)
Torsion Angle (Degrees), (=C-N+-C-C)
180 150
120 90
60 30
0 0 2 4 6 8 10
RHF/6-31G** MM3(94) MM2(91)
Torsion Angle (Degrees), (=C-N+-C-C)
Relative Energy (kcal/mol)
Supplemental Figure 6. RHF/6-31G**, MM3(94), and MM2(91) Side Chain Rotational
Pyridinium.
C4
C5 C6 N+1 C2
C3
H7
H11
H12 H10
H8
H9
Bond RHF/6-31G**a MM2 (91)b Difference MM3(94)b Difference
N+(1) - C(2) 1.3638 1.3520 -0.0118 1.3546 -0.0092
N+(1) - C(6) 1.3639 1.3521 -0.0118 1.3546 -0.0093
N+(1) - H(11) 1.0121 1.0128 0.0007 1.0140 0.0019
RMS Diffc 0.0077 0.0065
Bond Angle RHF/6-31G**d MM2 (91)e Difference MM3(94)e Difference C(2) - N+(1) - C(6) 123.139 122.742 -0.397 124.048 0.909 C(2) - N+(1) - H(11) 118.428 118.629 0.201 117.976 -0.452 C(6) - N+(1) - H(11) 118.428 118.629 0.201 117.976 -0.452 N+(1) - C(2) - C(3) 119.682 119.725 0.043 119.443 -1.239 N+(1) - C(2) - H(7) 116.761 116.376 -0.385 116.091 -0.670 N+(1) - C(6) - C(5) 119.682 119.727 0.045 118.443 -1.239 N+(1) - C(6) - H(12) 116.761 116.375 -0.386 116.091 -0.670
RMS Diff 0.212 0.659
________________
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to rg bond lengths based on MM3 (94) calculations of the pyridine and ethane structures.
N-ethylpyridinium
C4
C5 C6 N+1 C2
C3
H7
C11
H15 H10
H8
H9
C12
H14 H13
H18
H16 H17
Bond RHF/6-31G**a MM2(91)b Difference MM3(94)b Difference
N+(1) - C(2) 1.3641 1.3650 0.0009 1.3646 0.0005
N+(1) - C(6) 1.3641 1.3650 0.0009 1.3645 0.0004
N+(1) - C(11) 1.5037 1.4989 -0.0048 1.5062 0.0025
RMS Diffc 0.0060 0.0043
Bond Angle RHF/6-31G**d MM2(91)e Difference MM3(94)e Difference C(2) - N+(1) - C(6) 120.610 120.391 -0.219 120.106 -0.504 C(2) - N+(1) - C(11) 119.694 119.616 -0.078 119.944 0.250 C(6) - N+ (1) - C(11) 119.667 119.490 -0.177 119.944 0.277 N+(1) - C(2) - C(3) 121.198 120.743 -0.455 120.679 -0.519 N+(1) - C(2) - H(7) 116.528 117.294 0.766 115.584 -0.944 N+(1) - C(6) - C(5) 121.198 120.746 -0.452 120.679 -0.519 N+(1) - C(6) - H(15) 116.521 117.274 0.753 115.584 -0.937 N+(1) - C(11) - C(12) 111.709 111.426 -0.283 110.976 -0.733 N+(1) - C(11) - H(13) 106.838 107.618 0.780 106.988 0.150 N+(1) - C(11) - H(14) 106.795 107.538 0.743 106.988 0.193
RMS Diff 0.439 0.469
________________
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to rg bond lengths based on MM3(94) calculations of the pyridine and ethane structures.
bMM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as rg bond lengths.
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.
dRHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of pyridine and ethane.
N-n-propylpyridinium.
C4
C5 C6 N+1 C2 C3
H7
C13
H11
H10
H8
H9
C14
H16 H12
C15
H18
H17 H19
H20
H21
Bond RHF/6-31G**a MM2(91)b Difference MM3(94)b Difference
N+(1) - C(2) 1.3640 1.3650 0.0010 1.3644 0.0004
N+(1) - C(6) 1.3640 1.3650 0.0010 1.3644 0.0004
N+(1) - C(13) 1.5028 1.4990 -0.0038 1.5123 0.0095
RMS Diffc 0.0056 0.0051
Bond Angle RHF/6-31G**d MM2(91)e Difference MM3(94)e Difference C(2) - N+(1) - C(6) 120.585 120.395 -0.190 120.123 -0.462 C(2) - N+(1) - C(13) 119.700 119.461 -0.239 119.936 0.236 C(6) - N+(1) - C(13) 119.700 119.592 -0.108 119.936 0.236 N+(1) - C(2) - C(3) 121.216 120.748 -0.468 120.672 -0.544 N+(1) - C(2) - H(7) 116.500 117.280 0.780 115.570 -0.930 N+(1) - C(6) - C(5) 121.216 120.740 -0.476 120.672 -0.544 N+(1) - C(6) - H(11) 116.500 117.288 0.788 115.570 -0.930 N+(1) - C(13) - H(12) 106.910 107.517 0.607 106.871 -0.039 N+(1) - C(13) - C(14) 111.840 111.410 -0.430 111.011 -0.829 N+(1) - C(13) - H(16) 106.900 107.457 0.557 106.871 -0.029
RMS Diff 0.435 0.488
________________
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to rg bond lengths based on MM3(94) calculations of the pyridine and ethane structures.
bMM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as rg bond lengths.
N-isopropylpyridinium
C4
C5 C6 N+1 C2
C3
H7
C12
H11 H10
H8
H9
C13
H15
C14 H18
H19
H16 H17
H20
H21
Bond RHF/6-31G**a MM2(91)b Difference MM3(94)b Difference
N+(1) - C(2) 1.3631 1.3666 0.0035 1.3652 0.0021
N+(1) - C(6) 1.3653 1.3660 0.0007 1.3662 0.0009
N+(1) - C(12) 1.5217 1.5060 -0.0157 1.5222 0.0005
RMS Diffc 0.0069 0.0042
Bond Angle RHF/6-31G**d MM2(91)e Difference MM3(94)e Difference C(2) - N+(1) - C(6) 120.178 120.120 -0.058 119.710 -0.468 C(2) - N+(1) - C(12) 119.731 120.175 0.444 120.038 0.307 C(6) - N+(1) - C(12) 120.091 119.705 -0.386 120.251 0.160 N+(1) - C(2) - C(3) 121.483 120.836 -0.647 120.873 -0.610 N+(1) - C(2) - H(7) 116.676 117.770 1.094 115.912 -0.764 N+(1) - C(6) - C(5) 121.483 120.894 -0.589 120.907 -0.576 N+(1) - C(6) - H(11) 116.789 117.573 0.784 115.817 -0.972 N+(1) - C(12) - C(13) 110.377 111.471 1.094 110.633 0.256 N+(1) - C(12) - C(14) 110.352 111.439 1.087 110.633 0.281 N+(1) - C(12) - C(14) 104.112 107.023 2.911 105.585 1.473
RMS Diff 0.958 0.571
________________
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to rg bond lengths based on MM3(94) calculations of the pyridine and ethane structures.
bMM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as rg bond lengths.
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.
dRHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of pyridine and ethane.
s-trans- N-vinylmethyleneammonium
H5
C4
C3 N+2
H6 H8
C1
H9
H10
H7
Bond RHF/6-31G**a MM2(91)b Difference MM3(94) Difference
C(1) - N+(2) 1.3003 1.2892 -0.0111 1.2925 -0.0078
N+(2) - C(3) 1.4506 1.4390 -0.0116 1.4450 -0.0056
N+(2) - H(7) 1.0210 1.0130 -0.0080 1.0141 -0.0069
RMS Diffc 0.0082 0.0062
Bond Angle RHF/6-31G**d MM2(91)e Difference MM3(94) Difference N+(2) - C(1) - H(5) 119.988 118.943 -1.045 118.089 -1.899 N+(2) - C(1) - H(6) 119.699 117.269 -2.430 117.606 -2.093 C(1) - N+(2) - C(3) 126.019 126.305 0.286 127.437 1.418 C(1) - N+(2) - H(7) 117.853 117.126 -0.727 116.203 -1.650 C(3) - N+(2) - H(7) 116.128 116.569 0.441 116.361 0.233 N+(2) - C(3) - C(4) 120.840 121.153 0.313 121.858 1.018 N+(2) - C(3) - H(8) 114.206 116.695 2.489 114.703 0.497
RMS Diff 1.251 1.250
________________
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to rg bond lengths based on MM3(94) calculations of the pyridine and ethane structures.
bMM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as rg bond lengths.
s-trans- N-ethyl-N-vinylmethyleneammonium.
H12 C1
C2 N+3
H13 H8
C5
H6
H7
C4
C9
H10
H11
H16
H15 H14
Bond RHF/6-31G**a MM2(91)b Difference MM3(94)b Difference
C(2) - N+(3) 1.4607 1.4661 0.0054 1.4596 -0.0011
N+(3) - C(4) 1.4995 1.5040 0.0045 1.5086 0.0091
N+(3) - C(5) 1.3006 1.3015 0.0009 1.3011 0.0005
RMS Diffc 0.0067 0.0056
Bond Angle RHF/6-31G**d MM2(91)e Difference MM3(94)e Difference C(1) - C(2) - N+(3) 124.771 124.360 -0.411 124.772 0.001 N+(3) - C(2) - H(8) 112.916 115.858 2.942 113.944 1.028 C(2) - N+(3) - C(4) 120.379 120.038 -0.341 120.586 0.207 C(2) - N+(3) - C(5) 119.470 121.277 1.807 120.110 0.640 C(4) - N+(3) - C(5) 120.145 118.568 -1.577 119.303 -0.842 N+(3) - C(4) - C(9) 111.840 111.923 0.083 111.415 -0.425 N+(3) - C(4) - H(10) 106.385 108.359 1.974 107.268 0.883 N+(3) - C(4) - H(11) 111.187 107.605 0.776 107.026 0.197 N+(3) - C(5) - H(12) 120.363 118.802 -1.561 118.737 -1.626 N+(3) - C(5) - H(13) 120.098 119.494 -0.604 118.387 -1.711
RMS Diff 1.354 0.856
________________
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to rg bond lengths based on MM3(94) calculations of the N-vinyl-2-ethylidenimine (s-trans) and ethane structures.
bMM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as rg bond lengths.
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.
dRHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of N
-vinyl-2-ethylidenimine (s-trans) and ethane.
s-trans-N-n-propyl-N-vinylmethyleneammonium.
H18
C1 C2
N+3
H19
H10
C7 H8
H9
C4
C5 H12
H11
C6
H13
H14 H17 H15
H16
Bond RHF/6-31G**a MM2(91)b Difference MM3(94)b Difference
C(2) - N+(3) 1.4604 1.4662 0.0058 1.4595 -0.0009
N+(3) - C(4) 1.4987 1.5041 0.0054 1.5147 0.0160
N+(3) - C(7) 1.3005 1.3015 0.0010 1.3010 0.0005
RMS Diffc 0.0063 0.0063
Bond Angle RHF/6-31G**d MM2(91)e Difference MM3(94)e Difference C(1) - C(2) - N+(3) 124.807 124.363 -0.444 124.757 -0.050 N+(3) - C(2) - H(10) 112.911 115.854 2.943 113.947 1.036 C(2) - N+(3) - C(4) 120.471 120.037 -0.434 120.590 0.119 C(2) - N+(3) - C(7) 119.420 121.297 1.877 120.140 0.720 C(4) - N+(3) - C(7) 120.102 118.552 -1.550 119.269 -0.833 N+(3) - C(4) - C(5) 112.011 111.966 -0.045 111.444 -0.567 N+(3) - C(4) - H(11) 106.451 108.249 1.798 107.148 0.697 N+(3) - C(4) - H(12) 106.917 107.502 0.585 106.916 -0.001 N+(3) - C(7) - H(18) 120.054 119.474 -0.580 118.348 -1.706 N+(3) - C(7) - H(19) 120.393 118.805 -1.588 118.747 -1.646
RMS Diff 1.283 0.819
________________
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to rg bond lengths based on MM3(94) calculations of the N-vinyl-2-ethylidenimine (s-trans) and ethane structures.
bMM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as rg bond lengths.
s-trans- N-isopropyl-N-vinylmethyleneammonium.
H12
C1
C2 N+3
H13 H8
C5
H6
H7
C4 C9
C11
H10
H16
H15 H14
H19
H18 H17
Bond RHF/6-31G**a MM2(91)b Difference MM3(94)b Difference
C(2) - N+(3) 1.4624 1.4687 0.0063 1.4631 0.0007
N+(3) - C(4) 1.5186 1.5074 -0.0112 1.5232 0.0046
N+(3) - C(5) 1.3002 1.2975 -0.0027 1.2997 -0.0005
RMS Diffc 0.0078 0.0060
Bond Angle RHF/6-31G**d MM2(91)e Difference MM3(94)e Difference C(1) - C(2) - N+(3) 125.651 123.563 -2.088 124.494 -1.157 N+(3) - C(2) - H(8) 112.642 115.680 3.038 113.852 1.210 C(2) - N+(3) - C(4) 119.713 119.535 -0.178 120.387 0.674 C(2) - N+(3) - C(5) 118.430 121.057 2.627 119.539 1.109 C(4) - N+(3) - C(5) 121.838 119.394 -2.444 120.074 -1.764 N+(3) - C(4) - C(9) 108.960 110.952 1.992 110.172 1.212 N+(3) - C(4) - C(10) 112.196 112.872 0.676 111.722 -0.474 N+(3) - C(4) - H(11) 103.910 106.480 2.570 105.401 1.491 N+(3) - C(5) - H(12) 120.125 118.527 -1.598 118.487 -1.638 N+(3) - C(5) - H(13) 120.658 119.545 -1.113 118.743 -1.915
RMS Diff 1.856 1.220
________________
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to rg bond lengths based on MM3(94) calculations of the N-vinyl-2-ethylidenimine (s-trans) and ethane structures.
bMM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as rg bond lengths.
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.
dRHF/6-31G** bond angles are given in degrees (°) and are not scaled to the MM3(94) structures of N
-vinyl-2-ethylidenimine (s-trans) and ethane.
s-trans-N-n-butyl-N-vinylmethyleneammonium.
H13 C1
C2 N+3
H12
H11
C4 H10
H9
C5 C6 H15
H14
C7
H17
H16 C8
H19
H18
H20
H22
H21
Bond RHF/6-31G**a MM2(91)b Difference MM3(94)b Difference
C(2) - N+(3) 1.4602 1.4663 0.0061 1.4595 -0.0007
N+(3) - C(4) 1.3004 1.3015 0.0011 1.3010 0.0006
N+(3) - C(5) 1.4992 1.5041 0.0049 1.5147 0.0155
RMS Diffc 0.0062 0.0060
Bond Angle RHF/6-31G**d MM2(91)e Difference MM3(94)e Difference C(1) - C(2) - N+(3) 124.798 124.363 -0.435 124.754 -0.044 N+(3) - C(2) - H(11) 112.920 115.854 2.934 113.948 1.028 C(2) - N+(3) - C(4) 119.414 121.298 1.884 120.145 0.731 C(2) - N+(3) - C(5) 120.472 120.042 -0.430 120.583 0.111 C(4) - N+(3) - C(5) 120.108 118.545 -1.563 119.270 -0.838 N+(3) - C(4) - H(12) 120.401 118.805 -1.596 118.747 -1.654 N+(3) - C(4) - H(13) 120.040 119.474 -0.566 118.346 -1.694 N+(3) - C(5) - C(6) 112.003 111.935 -0.068 111.414 -0.589 N+(3) - C(5) - H(14) 106.393 108.227 1.834 107.146 0.753 N+(3) - C(5) - H(15) 106.864 107.489 0.625 106.886 0.022
RMS Diff 1.242 0.794
________________
aRHF/6-31G** bond lengths are given in angstroms (Å) and are scaled to rg bond lengths based on MM3(94) calculations of the N-vinyl-2-ethylidenimine (s-trans) and ethane structures.
bMM2(91) and MM3(94) bond lengths are given in angstroms (Å) and are reported as rg bond lengths.
for Pyridinium.
RHF/6-31G** MM3(94) Difference Assignment
3432.4 3426.2 6.2 N+-H stretching
3079.0 3081.3 -2.3 CH2 sym/sym stretch
3077.7 3079.9 -2.2 CH2 sym/asym stretch
3067.0 3068.9 -1.9 CH2 asym/sym stretch
3065.6 3065.0 0.6 CH2 asym/asym stretch
3048.0 3056.1 -8.1 CH2 sym str + N+-H str
--- 1696.7 --- Csp2-Csp2 asym stretch
1635.8 1638.5 -2.7 N+-Csp2 asym stretch
1631.6 1656.1 -24.5 Csp2-Csp2 asym stretch
1544.1 1509.8 34.3 CH2 asym wag
1482.8 1455.4 27.4 Csp2-Csp2 asym stretch
1378.4 1381.7 -3.3 CH2 sym wag
1291.7 1223.8 67.9 CH2 asym wag + N+-H wag
1197.6 1203.3 -5.7 CH2 asym wag
1185.0 1150.3 34.7 CH2 sym wag
1112.6 --- --- Csp2-Csp2 stretch
1052.1 1147.7 -95.6 CH2 out-of-plane wag
1044.4 978.9 65.5 N+-Csp2 symm stretch
1041.5 995.8 45.7 Csp2-Csp2 asym stretch
1016.6 1092.0 -75.4 CH2 out-of-plane wag
1012.6 935.5 77.1 Skeletal bending
1010.5 1026.7 -16.2 CH2 out-of-plane wag
980.4 911.7 68.7 Ring Breathing
883.4 818.6 64.8 CH2 out-of-plane wag
842.0 851.5 -9.5 CH2 out-of-plane wag
737.8 750.4 -12.6 CH2 out-of-plane bending
652.5 632.4 20.1 CH2 out-of-plane bending
621.2 581.5 39.7 Skeletal bending
596.8 584.5 12.3 Skeletal bending
395.4 397.4 -2.0 Ring twisting
383.1 425.6 -42.5 Ring deformation
for N-methylpyridinium
RHF/6-31G** MM3(94) Difference Assignment
3077.6 3079.2 -1.6 C-H sym/sym stretch
3075.1 3075.2 -0.1 C-H sym/asym stretch
3065.2 3067.3 -2.1 C-H asym/sym stretch
3062.7 3062.0 0.7 C-H asym/asym stretch
3048.5 3055.6 -7.1 C-H stretch
3018.1 2981.8 36.3 CH3 asym stretch
3004.9 2991.6 13.3 CH3 asym stretch
2916.6 2869.5 47.1 CH3 sym stretch
1649.0 1674.8 -25.8 Csp2=Csp2 sym stretch
--- 1676.6 --- Csp2=Csp2 + N+-Csp2 asym str
1602.6 1617.2 -14.6 Csp2=Csp2 + N+-Csp2 asym str
1501.7 1510.9 -9.2 Csp2=Csp2 + N+-Csp2 sym str
1491.0 1454.0 37.0 Csp2=Csp2 + N+-Csp2 asym str
1455.7 1385.8 69.9 CH3 asym bend
1448.6 1419.6 29.0 CH3 asym bend (C-H wagging)
1428.3 1420.9 7.4 CH3 sym bend
1361.6 1299.0 62.6 C-H sym wag (in-plane)
1222.1 1226.1 -4.0 C-H asym + CH3 wag (in-plane)
--- 1178.6 --- CH3 wag + CH out-of-plane bend
1203.3 1177.5 25.8 C-H asym wag (in-plane)
1177.5 1163.4 14.1 CH3 stretch + skeletal bend
1134.7 --- --- C-H wag + CH3 rocking
1127.9 1100.9 27.0 CH3 wagging (out-of-plane)
1107.5 --- --- Csp2=Csp2 asym stretch
1049.1 1112.8 -63.7 C-H asym wag (out-of-plane)
1042.5 980.6 61.9 Csp2=Csp2-Csp2 bending
1021.2 1044.4 -23.2 Csp2=Csp2 + N+-Csp2 asym str
1014.9 1116.1 -101.2 C-H asym wag (out-of-plane)
1008.2 931.4 76.8 Ring Breathing
991.3 996.2 -4.9 C-H sym wag (out-of-plane)
880.0 846.1 33.9 C-H asym wag (out-of-plane)
779.6 747.3 32.3 C-H sym wag (out-of-plane)
766.4 771.9 -5.5 Csp2=Csp2-Csp2 bending
664.4 664.8 -0.4 Ring out-of-plane deformation
636.6 581.1 55.5 Ring bending (in-plane)
514.4 509.2 5.2 Ring bending (in-plane)
438.8 447.8 -9.0 Ring bending (out-of-plane)
395.6 374.5 21.1 Ring twisting
373.9 406.1 -32.2 CH3 in-plane wag
for N-ethylpyridinium.
RHF/6-31G** MM3(94) Difference Assignment
3076.3 3078.6 -2.3 C-H sym/sym stretch
3073.9 3076.3 -2.4 C-H sym/asym stretch
3064.4 3067.6 -3.2 C-H asym/sym stretch
3061.8 3062.2 -0.4 C-H asym/asym stretch
3048.0 3055.7 -7.7 C-H stretch
2992.3 2948.1 44.2 CH2 asym stretch
2961.6 2969.9 -8.3 CH3 asym stretch
2950.6 2970.2 -19.6 CH3 asym stretch
2938.6 2892.3 46.3 CH2 sym stretch
2883.0 2874.0 9.0 CH3 sym stretch
1647.4 1678.7 -31.3 Csp2=Csp2 stretch
1603.4 1619.1 -15.7 Csp2=Csp2 + N+-Csp2 asym str
1503.9 1485.7 18.2 Csp2=Csp2 + N+-Csp2 sym str
1485.3 1676.6 -191.3 C-H wag (in-plane)
1471.5 1556.5 -85.0 CH2 + CH3 asym bend
1454.2 1433.0 21.2 CH2 + CH3 asym bend
--- 1459.9 --- CH3 asym bend
1452.4 1451.6 0.8 CH3 asym bend
1404.7 1452.6 -47.9 CH3 sym bend
1363.9 1353.2 10.7 C-H sym wag (in-plane)
1355.8 1370.6 -14.8 CH3 + CH2 wag
1283.9 --- --- C-H wag (in-plane) + CH2 wag
1202.0 1234.1 -32.1 C-H wag (in-plane)
1200.9 1176.7 24.2 C-H asym wag (in-plane)
1161.8 1190.7 -28.9 N+-Csp3 stretch
1141.6 1221.3 -79.7 C-H wag + CH2 wag (in-plane)
1105.4 1062.5 42.9 Csp2=Csp2 stretch
1081.6 1026.0 55.6 CH3 rock
1048.5 1154.5 -106.0 C-H wag (out-of-plane)
1042.7 --- --- Csp2=Csp2-Csp2(N+) asym bend
--- 1036.6 --- C-H asym wag (out-of-plane)
1038.8 1026.0 12.8 Csp2=Csp2 + N+-Csp2 sym str
1015.1 1116.1 -101.0 C-H asym wag (out-of-plane)
1008.3 931.0 77.3 Ring breathing
993.1 1000.5 -7.4 C-H asym wag (out-of-plane)
935.3 983.0 -47.7 Ring breathing + CH3 rock
880.8 846.6 34.2 C-H asym wag (out-of-plane)
787.1 787.8 -0.7 C-H sym wag (out-of-plane)
773.7 838.0 -64.3 CH2 + CH3 wag
739.8 754.4 -14.6 Ring bending (Csp2=Csp2-Csp2)
672.8 665.0 7.8 Ring out-of-plane deformation
636.6 581.2 55.4 Ring bending
536.0 540.3 -4.3 Ring bending
470.4 459.7 10.7 Ring bending (Csp2-N+=Csp2)
396.4 375.3 21.1 Ring twisting
379.2 406.2 -27.0 Ethyl in-plane bending
310.2 329.1 -18.9 Ethyl bending + ring bending
217.9 218.8 -0.9 CH3 torsion
129.7 135.2 -5.5 Ethyl bending
50.7 58.5 -7.8 Ethyl torsion
for N-n-propylpyridinium
RHF/6-31G** MM3(94) Difference Assignment
3076.8 3078.7 -1.9 C-H sym/sym stretch
3074.3 3076.5 -2.2 C-H sym/asym stretch
3064.6 3067.6 -3.0 C-H asym/sym stretch
3062.0 3062.3 -0.3 C-H asym/asym stretch
3047.8 3055.7 -7.8 C-H stretch
2985.0 2949.4 35.6 CH2 asym stretch
2956.3 2968.6 -12.3 CH3 asym stretch
2938.4 2970.2 -31.8 CH3 asym stretch
2932.5 2891.3 41.2 CH2 sym stretch
2909.6 2924.9 -15.3 CH2 asym stretch
2876.6 2867.6 9.0 CH2 sym stretch
2875.1 2881.3 -6.2 CH3 sym stretch
1647.7 1679.5 -31.8 Csp2=Csp2 stretch
1603.4 1619.2 -15.8 Csp2=Csp2 + N+-Csp2 asym str
1503.5 1487.8 15.7 Csp2=Csp2 + N+-Csp2 sym str
1485.0 1676.6 -191.6 Csp2=Csp2 + N+-Csp2 asym str
1476.2 1458.3 17.9 CH2 + CH3 asym bend
1463.0 1456.9 6.0 CH3 asym bend
1462.9 1453.8 9.1 CH2 + CH3 asym bend
1455.3 1439.1 16.2 CH2 + CH3 asym bend
--- 1452.9 --- CH2 + CH3 asym bend
1403.7 1395.4 8.3 CH3 wag
1379.8 1569.1 -189.3 CH2 asym wag
1363.6 1357.3 6.3 C-H sym wag (in-plane)
1305.6 1351.6 -46.0 CH2 asym wag
1299.6 1224.6 75.0 CH2 sym wag
1261.3 1240.2 21.1 CH2 asym wag
1200.9 1175.5 25.4 C-H wag (in-plane)
1196.7 1221.9 -25.2 C-H asym wag (in-plane)
1160.0 1185.2 -25.2 N+-Csp3 stretch
1145.3 1033.7 111.6 C-H asym wag (in-plane)
1104.7 --- --- C-H sym wag (in-plane)
1098.9 1060.1 38.8 CH2-CH2 stretch
1048.1 1155.0 -106.9 C-H asym bend (out-of-plane)
1043.8 1058.8 -15.0 C-H sym wag (in-plane)
1042.9 981.2 61.7 Ring bending (Csp2=Csp2-Csp2)
1015.0 1116.2 -101.2 C-H wag (out-of-plane)
1008.3 931.7 76.6 Ring breathing
994.3 1015.4 -21.1 C-H wag (out-of-plane)
993.7 993.0 0.7 Csp3-Csp3-Csp3 bending
881.0 846.7 34.3 C-H sym wag (out-of-plane)
876.6 899.7 -23.1 Csp3-Csp3-Csp3 bending
860.3 902.6 -42.3 CH2 + CH3 bending
794.2 762.8 31.4 Ring deformation (out-of-plane)
--- 803.1 --- Ring deformation (in-plane)
for N-n-propylpyridinium (continued)
RHF/6-31G** MM3(94) Difference Assignment
468.8 461.5 7.3 Ring deformation (out-of-plane)
396.6 375.0 21.6 Ring twisting
372.5 397.1 -24.6 CH2 wag
301.8 300.3 1.5 CH3 wag
266.3 295.3 -29.0 Propyl wag
225.5 227.5 -2.0 CH3 twisting
99.5 106.2 -6.8 CH2-CH2 bending
83.7 50.3 33.4 CH2-CH2 torsion
49.0 57.1 -8.1 Propyl torsion
for N-isopropylpyridinium
RHF/6-31G** MM3(94) Difference Assignment
3090.8 3088.2 2.6 C-H sym/sym stretch
3078.7 3079.5 -0.8 C-H sym/asym stretch
3066.1 3068.7 -2.6 C-H asym/sym stretch
3063.0 3062.7 0.3 C-H asym/asym stretch
3047.8 3055.9 -8.1 C-H stretch
2965.5 2977.0 -11.5 CH3 sym/asym stretch
2962.2 2969.6 -7.4 CH3 sym/asym stretch
2959.5 2968.1 -8.6 CH3 asym/asym stretch
2950.4 2976.2 -25.8 CH3 asym/asym stretch
2941.7 2930.7 11.0 C-H isopropyl stretch
2885.5 2879.0 6.5 CH3 sym/sym stretch
2882.2 2880.2 2.1 CH3 asym/sym stretch
1645.7 1675.8 -30.1 Csp2=Csp2 stretch
1603.4 1628.8 -25.4 Csp2=Csp2 + N+-Csp2 asym str
--- 1680.9 --- C-H wag (in-plane)
1500.2 1496.6 3.6 Csp2=Csp2 + N+-Csp2 sym str
1485.9 1553.4 -67.5 Csp2=Csp2 + N+-Csp2 asym str
1466.8 1471.6 -4.8 CH3 sym/asym bending
1462.9 1469.4 -6.5 CH3 sym/asym bending
1454.0 1459.3 -5.3 CH3 asym/asym bending
1445.9 1457.0 -11.1 CH3 asym/asym bending
1415.4 1409.0 6.4 CH3 sym/sym bending
1397.6 1443.8 -46.2 CH3 asym/sym bending
1380.7 1431.2 -50.5 C-H wag (in-plane)
1338.5 1287.0 51.5 C-H isopropyl wag
1326.9 1343.2 -16.3 C-H isopropyl wag
1203.7 1184.7 19.0 C-H asym wag (in-plane)
1201.7 1227.3 -25.6 C-H asym wag (in-plane)
1175.7 1091.2 84.5 C-H asym wag (in-plane)
1143.6 1211.3 -67.7 N+-Csp2 stretch
1122.5 1092.1 30.4 CH3 asym stretch
1108.8 1037.2 71.6 Ring bending (Csp2=Csp2-Csp2)
1095.0 1032.5 62.5 Ring bending (Csp2=Csp2-Csp2)
1048.4 1160.0 -111.6 C-H wag (out-of-plane)
1046.7 974.1 72.6 Ring bending (Csp2=Csp2-Csp2)
1039.3 930.1 109.2 Ring deformation (in-plane)
1016.1 1116.3 -100.2 C-H wag (out-of-plane)
1006.6 --- --- Ring breathing
994.8 1009.5 -14.7 C-H wag (out-of-plane)
926.1 940.7 -14.6 CH3 asym wag
918.6 971.1 -52.5 CH3 asym wag
879.7 847.6 32.1 C-H wag (out-of-plane)
860.9 870.1 -9.2 CH3 sym wag
790.0 782.0 8.0 C-H wag (out-of-plane)
712.0 737.6 -25.6 Ring deformation (in-plane)
for N-isopropylpyridinium (continued)
RHF/6-31G** MM3(94) Difference Assignment
398.6 379.9 18.7 Ring twisting
322.0 344.7 -22.7 CH3 asym twisting
297.2 302.7 -5.5 CH3 sym twisting
254.0 237.1 16.9 CH3 torsion (sym)
226.1 255.5 -29.4 Isopropyl rocking
222.8 233.5 -10.7 CH3 torsion (asym)
121.1 125.6 -4.5 Isopropyl wag
43.6 55.7 -12.1 Isopropyl torsion
for s-trans-N-vinylmethyleneammonium
RHF/6-31G** MM3(94) Difference Assignment
3387.5 3422.4 -34.9 N+-H stretching
3113.2 3135.0 -21.8 CH2 asym stretch
3096.2 3112.7 -16.5 CH2 asym stretch
3068.0 3069.4 -1.4 C-H stretch
3002.8 3021.8 -19.0 CH2 sym stretch
3001.8 3014.1 -12.3 CH2 sym stretch
1724.9 1747.6 -22.7 N+-Csp2 stretch
1663.4 1589.1 74.3 Csp2-Csp2 stretch
1487.7 1426.7 61.0 CH2 scissor
1409.4 1413.5 -4.1 N+-H wag
1389.1 1241.2 147.9 CH2 wag
1302.7 1195.4 107.3 C-H wag
1213.5 1147.9 65.6 CH2 wag
1137.2 1134.6 2.6 CH2 out-of-plane wag
1039.7 997.1 42.6 CH2 in-plane wag
1028.3 1071.2 -42.9 CH2 out-of-plane wag
1021.0 1051.5 -30.5 CH2 out-of-plane wag
940.5 994.0 -53.5 N+-H + CH2 out-of-plane wag
848.4 864.5 -16.1 CH2 in-plane wag
747.4 812.4 -65.0 Vinyl wag
527.8 500.1 27.7 N+-Csp2=Csp2 bend
510.5 581.3 -70.8 CH2 twist
314.6 352.8 -38.3 Csp2-N+-Csp2 bend
129.6 139.2 -9.6 Skeletal torsion
for s-trans-N-methyl-N-vinylmethyleneammonium
RHF/6-31G** MM3(94) Difference Assignment
3115.3 3137.2 -21.9 CH2 asym stretch
3105.2 3118.1 -12.9 CH2 asym stretch
3065.0 3059.5 5.5 C-H stretch
3023.3 3027.2 -3.9 CH2 sym + CH3 asym stretch
3020.4 2990.2 30.2 CH2 sym str + CH3 asym str
3010.7 2985.0 25.7 CH3 asym stretch
3007.6 3017.9 -10.3 CH2 sym stretch
2919.4 2870.5 48.9 CH3 sym stretch
1720.4 1669.6 50.8 N+=Csp2 stretch
1669.1 1553.5 115.6 Csp2=Csp2 stretch
1487.8 1410.1 77.7 CH2 scissor + CH3 asym bend
1446.7 1437.2 9.5 CH2 asym bend + CH2 scissor
1444.1 1440.0 4.1 CH3 asym bend
1427.8 --- --- CH3 sym bend
1401.3 1471.9 -70.6 CH2 scissor
1344.0 1294.9 49.1 C-H wag (in-plane) + N+-CH3 str
--- 1285.7 --- CH2 scissor
1300.4 1234.0 66.4 C-H wag (in-plane) + N+-CH3 str
1137.5 1245.5 -108.0 CH3 rock + CH2 wag
(out-of-plane)
1123.1 1142.8 -19.7 CH2 wag (out-of-plane) + CH3
rock
1118.4 1099.4 19.0 CH3 wag
1065.7 1047.7 18.0 CH2 asym wag (in-plane)
1023.5 1124.4 -100.9 CH2 wag (out-of-plane)
961.6 1069.4 -107.8 C-H wag (out-of-plane) + CH2
twist
932.3 905.0 27.3 CH2 sym wag (in-plane)
--- 968.4 --- CH2 twist
759.8 723.2 36.6 CH2 sym twist
753.6 783.4 -29.8 N+-Csp2 + N+-CH3 stretch
631.0 --- --- CH2 twist
534.7 539.8 -5.1 Csp2=Csp2-N+ bend
473.2 501.4 -28.2 Csp2-N+=Csp2 bend
393.0 492.2 -99.2 N+ out-of-plane bend
308.2 325.1 -16.9 Csp2=Csp2-N+ bend
216.5 256.0 -39.5 CH3 torsion
107.3 96.9 10.4 Skeletal torsion
for s-trans-N-ethyl-N-vinylmethyleneammonium
RHF/6-31G** MM3(94) Difference Assignment
3112.1 3137.2 -25.1 CH2 asym stretch
3105.9 3121.2 -15.3 CH2 asym stretch
3061.5 3058.0 3.5 C-H stretch
3022.7 3029.3 -6.7 CH2 sym stretch
3006.9 3017.8 -10.9 CH2 sym str + Csp3-H asym str
3002.2 2954.6 47.6 Csp3-H asym str
2973.4 2977.2 -3.8 CH3 asym stretch
2959.6 2969.3 -9.7 CH3 asym stretch
2947.9 2897.5 50.4 Csp3-H sym stretch
2891.2 2877.6 13.7 CH3 sym stretch
1716.1 1672.9 43.2 N+-Csp2 + Csp2=Csp2 stretch
1669.0 1586.9 82.1 Csp2=Csp2 + N+-Csp2 stretch
1491.8 1468.7 23.1 CH2 scissor
1462.8 1526.2 -63.4 CH3 asym bend + CH2 scissor
1458.3 1456.1 2.2 CH3 asym bend + CH2 scissor
1452.0 1460.2 -8.2 CH3 asym bend
1405.7 1442.5 -36.8 CH3 sym bend + CH2 scissor
1404.0 1387.1 16.9 CH3 sym bend + CH2 scissor
1361.6 1314.1 47.5 CH2 (ethyl) asym bend
1342.6 1370.3 -27.7 C-H wag + CH2 asym bend
1305.3 1240.0 65.3 C-H wag + CH2 (ethyl) wag
1248.9 1210.8 38.1 CH2 (ethyl) + CH2 wag (in-plane)
1137.9 1065.0 72.9 CH3 rock
1127.7 1232.4 -104.7 CH2 wag (out-of-plane)
1085.0 1042.9 42.0 CH3 wag
1067.3 1027.2 40.1 CH2 asym wag (in-plane)
1021.3 1123.4 -102.1 CH2 wag (out-of-plane)
967.0 1077.5 -110.5 C-H wag (out-of-plane) + CH2
twist
961.1 996.3 -35.2 Csp3-Csp3 stretch
890.4 897.6 -7.2 CH2 sym wag (in-plane)
786.7 854.9 -68.2 Ethyl wag
762.1 942.2 -180.1 CH2 twisting
709.9 776.5 -66.6 Csp2-N+ str + CH3 rock
655.9 728.8 -72.9 CH2 twist
535.4 549.1 -13.7 Csp2=N+-Csp2 bend
472.4 528.4 -56.0 N+ out-of-plane bend
465.1 494.1 -29.0 CH2 wag (in-plane)
330.1 352.8 -22.7 Csp2=Csp2-N+ bend
241.0 272.1 -31.1 Csp3-Csp3-N+ bend
for s-trans-N-n-propyl-N-vinylmethyleneammonium
RHF/6-31G** MM3(94) Difference Assignment
3112.4 3137.4 -25.0 CH2 asymmetric stretch
3106.2 3121.1 -14.9 CH2 asymmetric stretch
3061.3 3058.1 3.2 C-H stretch
3022.7 3029.2 -6.5 CH2 symmetric stretch
3006.7 3017.9 -11.2 CH2 symmetric stretch
2997.0 2956.1 40.9 CH2 asymmetric stretch
2958.2 2968.6 -10.4 CH3 asymmetric stretch
2945.3 2970.2 -24.9 CH3 asymmetric stretch
2941.1 2883.4 57.7 CH2 asymmetric stretch
2925.0 2930.8 -5.8 CH2 asymmetric stretch
2887.5 2896.8 -9.3 CH2 symmetric stretch
2875.6 2870.2 5.4 CH3 symmetric stretch
1716.1 1672.9 43.2 N+-C stretch
1669.2 1531.6 137.6 CH2 scissor
1491.2 1595.3 -104.1 CH2 twist
1473.7 1456.5 17.3 CH2 twist
1463.0 1456.4 6.5 CH3 twist
1458.5 1452.4 6.1 CH3 symmetric stretch
--- 1476.0 --- CH3 symmetric stretch
1457.5 1442.9 14.6 CH2 bend
1404.5 1375.6 28.9 CH2 scissor
1404.0 1408.4 -4.4 CH3 umbrella
1380.0 1355.9 24.1 CH2 twist/CH3 umbrella
1347.6 1315.6 32.0 CH2 scissor/CH wag
1314.5 1240.8 73.7 C-H bend (out-of-plane)
1297.2 --- --- C-H bend (out-of-plane)
1290.0 1232.9 57.1 CH wag
1228.8 1228.5 0.3 CH2, CH3 twist
1145.4 1212.1 -66.7 CH2, CH3 rock
1126.5 1123.4 3.1 C-H wag (out-of-plane)
1099.1 1064.6 34.5 CH3 twist
1067.9 1054.4 13.5 CH2 twist
1020.2 1078.0 -57.8 CH2 twist (out-of-plane)
--- 1039.6 --- CH2 twist
991.6 994.9 -3.3 C-C-C stretch
965.5 979.9 -14.4 CH2 wag
926.4 919.9 6.5 CH3 twist
878.8 --- --- CH2 twist
866.1 908.0 -41.9 CH2 twist
766.8 895.3 -128.5 CH2 twist
758.0 809.2 -51.2 CH2 twist
728.2 794.6 -66.4 H-C-H bend
648.4 730.9 -82.5 CH2 twist
for s-trans-N-n-propyl-N-vinylmethyleneammonium (continued)
RHF/6-31G** MM3(94) Difference Assignment
474.9 524.1 -49.2 CH2 wag
454.8 506.4 -51.6 CH2 wag
355.3 363.7 -8.4 CH2 wag
285.9 301.0 -15.1 CH2 wag
226.4 229.4 -3.0 CH3 twist
186.9 217.7 -30.8 N+ bend (out-of-plane)
113.3 128.1 -14.8 CH=CH2 wag
86.0 80.9 5.0 C-N+-C-C torsion
75.4 45.8 29.6 C-N+-C-C torsion
for s-trans-N-isopropyl-N-vinylmethyleneammonium
RHF/6-31G** MM3(94) Difference Assignment
3127.1 3146.9 -19.8 CH2 asymmetric stretch
3107.0 3118.7 -11.7 CH2 asymmetric stretch
3059.6 3057.3 2.2 C-H stretch
3023.6 3027.5 -3.9 CH2 symmetric stretch
3017.4 3025.6 -8.2 CH2 asymmetric stretch
2985.7 2948.7 37.0 CH3 asymmetric stretch
2970.5 2973.2 -2.7 CH3 asymmetric stretch
2962.1 2970.8 -8.7 CH3 asymmetric stretch
2953.9 2967.3 -13.4 CH3 asymmetric stretch
2949.7 2978.7 -28.9 CH3 asymmetric stretch
2887.6 2878.8 8.8 CH2 asymmetric stretch
2882.0 2880.3 1.7 CH3 symmetric stretch
1715.5 1673.1 42.4 N+-C stretch
--- 1573.1 --- C-H wag
1669.9 1544.7 125.2 CH wag, C-C stretch
1478.2 1484.8 -6.6 CH2 scissor
1470.6 1465.1 5.5 CH3 twist
1461.9 --- --- CH3 twist
1452.7 1461.1 -8.4 CH3 twist
1448.4 1458.4 -10.0 CH3 twist
1417.4 1452.7 -35.3 CH2 scissor
1411.0 1442.1 -31.1 CH3 bend (out-of-plane)
--- 1324.3 --- CH3 bend (out-of-plane)
1395.5 1409.3 -13.8 CH3 umbrella
1359.9 1347.0 12.9 C-H wag
1343.7 1250.0 93.7 CH2 scissor
1322.0 --- --- C-H wag
1275.2 --- --- C-N+-C bend
1171.5 1067.4 104.1 CH3 twist
1130.3 1236.0 -105.7 CH wag, CH2 bend (out-of-plane)
1124.5 1228.3 -103.8 CCC bend
1101.8 1129.9 -28.1 CH3 twist
1065.9 1069.8 -3.9 CH2 wag
1018.5 1026.8 -8.3 CH2 twist
967.3 1107.6 -140.3 CH wag, CH2 scissor
929.9 935.4 -5.5 CH3 umbrella
--- 978.6 --- CH3 twist
925.7 966.0 -40.3 CH3 twist
902.5 903.3 -0.8 CH2 wag
845.2 1091.4 -246.2 CH2 twist
762.2 859.3 -97.1 CH2 twist
694.2 757.2 -63.0 CCC bend
656.4 723.0 -66.6 CH2 twist
532.2 575.2 -43.0 CH2 wag
511.2 538.9 -27.7 CH2 wag
472.9 481.9 -9.0 CH2 wag
for s-trans-N-isopropyl-N-vinylmethyleneammonium (continued)
RHF/6-31G** MM3(94) Difference Assignment
337.2 334.0 3.2 C-C-N+-C torsion
284.9 254.2 30.7 CH3 rotation
266.5 289.5 -23.0 CH3 twist
233.6 245.2 -11.6 C-N+-C-C torsion
209.4 222.5 -13.1 CH3 twist
101.3 104.5 -3.2 H-C-C-H bend
61.3 50.5 10.8 CH3 bend
