This journal is © The Owner Societies 2002

Table S1: Theoretical and experimental geometry data of cis-3-fluorostyrene (distances in Å and angles in º )

HF / MP2 / B3PW91 / B3LYP
6-31G* / 6-31G* / 6-31G* / 6-311G** / 6-311++G** / 6-31G* / 6-311G** / 6-311++G** / Exp.[8]
C1-C2 / 1.3945 / 1.4037 / 1.4038 / 1.4012 / 1.4017 / 1.4062 / 1.4038 / 1.4045 / 1.395
C1-C3 / 1.4805 / 1.4719 / 1.4690 / 1.4677 / 1.4679 / 1.4721 / 1.4715 / 1.4717 / 1.475
C3-C4 / 1.3216 / 1.3426 / 1.3377 / 1.3341 / 1.3351 / 1.3386 / 1.3349 / 1.3362 / 1.340
C2-C5 / 1.3739 / 1.3866 / 1.3836 / 1.3799 / 1.3795 / 1.3850 / 1.3814 / 1.3809 / 1.383
C5-C6 / 1.3801 / 1.3904 / 1.3908 / 1.3875 / 1.3870 / 1.3923 / 1.3890 / 1.3885 / 1.383
C6-C7 / 1.3827 / 1.3957 / 1.3921 / 1.3892 / 1.3898 / 1.3942 / 1.3914 / 1.3922 / 1.395
C7-C8 / 1.3860 / 1.3951 / 1.3927 / 1.3900 / 1.3904 / 1.3948 / 1.3922 / 1.3929 / 1.397
C8-C1 / 1.3919 / 1.4044 / 1.4038 / 1.4009 / 1.4010 / 1.4059 / 1.4033 / 1.4035 / 1.397
C2-H9 / 1.0728 / 1.0860 / 1.0849 / 1.0833 / 1.0833 / 1.0845 / 1.0823 / 1.0823 / 1.081
C3-H10 / 1.0774 / 1.0899 / 1.0901 / 1.0883 / 1.0884 / 1.0897 / 1.0874 / 1.0874 / 1.092
C4-H11 / 1.0746 / 1.0848 / 1.0859 / 1.0840 / 1.0841 / 1.0856 / 1.0831 / 1.0832 / 1.088
C4-H12 / 1.0750 / 1.0859 / 1.0871 / 1.0853 / 1.0854 / 1.0868 / 1.0844 / 1.0844 / 1.089
C5-F13 / 1.3310 / 1.3593 / 1.3456 / 1.3465 / 1.3495 / 1.3512 / 1.3531 / 1.3573 / 1.354
C6-H14 / 1.0736 / 1.0856 / 1.0852 / 1.0834 / 1.0835 / 1.0848 / 1.0825 / 1.0825 / 1.081
C7-H15 / 1.0750 / 1.0871 / 1.0867 / 1.0847 / 1.0848 / 1.0864 / 1.0838 / 1.0838 / 1.083
C8-H16 / 1.0753 / 1.0880 / 1.0873 / 1.0852 / 1.0853 / 1.0868 / 1.0843 / 1.0843 / 1.080
C2-C1-C3 / 122.465 / 121.722 / 122.724 / 122.637 / 122.641 / 122.735 / 122.672 / 122.678 / -
C8-C1-C3 / 118.952 / 119.465 / 118.944 / 119.002 / 118.979 / 118.966 / 119.033 / 119.003 / 118
C1-C3-C4 / 127.026 / 125.439 / 127.427 / 127.332 / 127.351 / 127.463 / 127.418 / 127.436 / 127
C1-C2-C5 / 119.325 / 119.082 / 119.511 / 119.473 / 119.324 / 119.477 / 119.460 / 119.283 / 117.9
C2-C5-C6 / 122.749 / 122.836 / 122.582 / 122.634 / 122.880 / 122.669 / 122.722 / 123.018 / 123.4
C5-C6-C7 / 117.877 / 117.929 / 117.965 / 117.966 / 117.812 / 117.932 / 117.927 / 117.745 / 117.9
C6-C7-C8 / 120.583 / 120.474 / 120.524 / 120.512 / 120.527 / 120.501 / 120.493 / 120.510 / 120.5
C7-C8-C1 / 120.883 / 120.866 / 121.086 / 121.054 / 121.076 / 121.121 / 121.103 / 121.126 / 119.8
C8-C1-C2 / 118.583 / 118.812 / 118.332 / 118.362 / 118.380 / 118.299 / 118.294 / 118.876 / 120.5
C5-C2-H9 / 118.721 / 119.203 / 118.722 / 118.671 / 118.860 / 118.751 / 118.655 / 118.876 / 120.0
C1-C2-H9 / 121.954 / 121.715 / 121.767 / 121.856 / 121.8157 / 121.771 / 121.884 / 121.842 / -
C4-C3-H10 / 118.325 / 118.766 / 18.113 / 118.173 / 118.150 / 118.147 / 118.147 / 118.123 / 118.1
C1-C3-H10 / 114.640 / 115.767 / 114.459 / 114.495 / 114.499 / 114.389 / 114.434 / 114.441 / -
C3-C4-H11 / 120.768 / 121.072 / 120.836 / 120.783 / 120.735 / 120.880 / 120.829 / 120.763 / 121.1
C3-C4-H12 / 123.028 / 122.265 / 122.959 / 122.790 / 122.848 / 122.947 / 122.819 / 122.882 / 123.1
C2-C5-H13 / 118.582 / 118.537 / 118.694 / 118.667 / 118.558 / 118.654 / 118.621 / 118.491 / -
C7-C6-H14 / 122.235 / 122.262 / 122.208 / 122.245 / 122.214 / 122.264 / 122.283 / 122.249 / 122.1
C5-C6-H14 / 119.887 / 119.809 / 119.827 / 119.789 / 119.974 / 119.803 / 119.789 / 120.006 / -
C8-C7-H15 / 119.796 / 119.957 / 119.889 / 119.920 / 119.921 / 119.882 / 119.915 / 119.916 / 119.9
C6-C7-H15 / 119.621 / 119.569 / 119.588 / 119.569 / 119.552 / 119.617 / 119.592 / 119.574 / -
C1-C8-H16 / 119.538 / 119.316 / 119.181 / 119.158 / 119.178 / 119.157 / 119.165 / 119.188 / 120.1
C7-C8-H16 / 119.580 / 119.818 / 119.733 / 119.788 / 119.746 / 119.722 / 119.732 / 119.687 / -
C2-C1-C3-C4 / 14.132 / 25.397 / 0.0 / 0.0 / 0.0 / 0.0 / 0.0 / 0.0 / 0.0
E/Hartrees / -406.4370670 / -407.6126092 / -408.7258243 / -408.8276607 / -408.8344535 / -408.8818788 / -408.9918077 / -408.9997628

Table S2: Structural parameters of trans-3-fluorostyrene (distances in Å and angles in º )

HF / MP2 / B3PW91 / B3LYP
6-31G* / 6-31G* / 6-31G* / 6-311G** / 6-311++G** / 6-31G* / 6-311G** / 6-311++G** / Exp.[8]
C1-C2 / 1.3912 / 1.4032 / 1.4021 / 1.3994 / 1.3999 / 1.4043 / 1.4018 / 1.4028 / 1.395
C1-C3 / 1.4810 / 1.4724 / 1.4696 / 1.4683 / 1.4686 / 1.4727 / 1.4721 / 1.4723 / 1.475
C3-C4 / 1.3215 / 1.3426 / 1.3377 / 1.3341 / 1.3351 / 1.3386 / 1.3348 / 1.3362 / 1.340
C2-C5 / 1.3779 / 1.3876 / 1.3873 / 1.3840 / 1.3837 / 1.3887 / 1.3855 / 1.3849 / 1.383
C5-C6 / 1.3757 / 1.3892 / 1.3869 / 1.3832 / 1.3827 / 1.3884 / 1.3847 / 1.3840 / 1.383
C6-C7 / 1.3871 / 1.3968 / 1.3961 / 1.3936 / 1.3942 / 1.3983 / 1.3959 / 1.3966 / 1.395
C7-C8 / 1.3823 / 1.3944 / 1.3894 / 1.3863 / 1.3866 / 1.3914 / 1.3884 / 1.3892 / 1.397
C8-C1 / 1.3951 / 1.4049 / 1.4056 / 1.4028 / 1.4029 / 1.4080 / 1.4055 / 1.4055 / 1.397
C2-H9 / 1.0744 / 1.0871 / 1.0863 / 1.0845 / 1.0846 / 1.0859 / 1.0836 / 1.0836 / 1.081
C3-H10 / 1.0775 / 1.0899 / 1.0902 / 1.0883 / 1.0885 / 1.0898 / 1.0875 / 1.0875 / 1.092
C4-H11 / 1.0747 / 1.0848 / 1.0859 / 1.0840 / 1.0841 / 1.0856 / 1.0831 / 1.0832 / 1.088
C4-H12 / 1.0750 / 1.0858 / 1.0869 / 1.0851 / 1.0851 / 1.0866 / 1.0841 / 1.0841 / 1.089
C5-F13 / 1.3307 / 1.3590 / 1.3449 / 1.3457 / 1.3485 / 1.3504 / 1.3522 / 1.3569 / 1.354
C6-H14 / 1.0736 / 1.0856 / 1.085 / 1.0832 / 1.0833 / 1.0847 / 1.0824 / 1.0825 / 1.081
C7-H15 / 1.0751 / 1.0871 / 1.0869 / 1.0849 / 1.0851 / 1.0866 / 1.0841 / 1.0840 / 1.083
C8-H16 / 1.0736 / 1.0868 / 1.0857 / 1.0837 / 1.0838 / 1.0852 / 1.0827 / 1.0828 / 1.080
C2-C1-C3 / 118.546 / 119.001 / 118.423 / 118.431 / 118.414 / 118.457 / 118.456 / 118.434 / -
C8-C1-C3 / 122.853 / 122.187 / 123.262 / 123.221 / 123.216 / 123.259 / 123.257 / 123.263 / 123
C1-C3-C4 / 126.770 / 125.201 / 127.388 / 127.295 / 127.272 / 127.443 / 127.405 / 127.379 / 127
C1-C2-C5 / 119.649 / 119.362 / 119.909 / 119.869 / 119.713 / 119.869 / 119.849 / 119.654 / 117.9
C2-C5-C6 / 122.421 / 122.553 / 122.182 / 122.222 / 122.472 / 122.283 / 122.322 / 122.633 / 123.4
C5-C6-C7 / 117.864 / 117.932 / 117.925 / 117.931 / 117.774 / 117.888 / 117.889 / 117.722 / 117.9
C6-C7-C8 / 120.931 / 120.754 / 120.973 / 120.968 / 120.981 / 120.942 / 120.943 / 120.925 / 120.5
C7-C8 -C1 / 120.533 / 120.587 / 120.695 / 120.662 / 120.689 / 120.734 / 120.711 / 120.763 / 119.8
C8-C1-C2 / 118.601 / 118.812 / 118.315 / 118.349 / 118.370 / 118.284 / 118.286 / 118.303 / 120.5
C5-C2-H9 / 119.044 / 119.348 / 119.124 / 119.130 / 119.312 / 119.136 / 119.110 / 119.323 / 120.0
C1-C2-H9 / 121.307 / 121.290 / 120.967 / 121.001 / 120.974 / 120.995 / 121.041 / 121.023 / -
C4-C3-H10 / 118.384 / 118.800 / 118.060 / 118.097 / 118.071 / 118.092 / 118.069 / 118.045 / 118.1
C1-C3-H10 / 114.834 / 115.970 / 114.552 / 114.608 / 114.656 / 114.465 / 114.526 / 114.576 / -
C3-C4-H11 / 120.799 / 121.088 / 120.788 / 120.728 / 120.694 / 120.831 / 120.770 / 120.722 / 121.1
C3-C4-H12 / 122.925 / 122.194 / 122.992 / 122.823 / 122.852 / 122.987 / 122.860 / 122.887 / 123.1
C2-C5-H13 / 118.567 / 118.627 / 118.708 / 118.679 / 118.572 / 118.665 / 118.632 / 118.495 / -
C7-C6-H14 / 122.124 / 122.212 / 122.082 / 122.109 / 122.086 / 122.136 / 122.147 / 122.125 / 122.1
C5-C6-H14 / 120.011 / 119.856 / 119.992 / 119.960 / 120.140 / 119.976 / 119.964 / 120.143 / -
C8-C7-H15 / 119.664 / 119.810 / 119.714 / 119.757 / 119.757 / 119.707 / 119.751 / 119.760 / 119.9
C6-C7-H15 / 119.404 / 119.436 / 119.313 / 119.275 / 119.262 / 119.352 / 119.306 / 119.315 / -
C1-C8-H16 / 120.112 / 119.668 / 119.978 / 120.021 / 120.042 / 119.931 / 120.013 / 120.033 / 120.1
C7-C8-H16 / 119.355 / 119.745 / 119.327 / 119.317 / 119.269 / 119.335 / 119.276 / 119.204 / -
C2-C1-C3-C4 / 161.914 / 152.466 / 180.0 / 180.0 / 180.0 / 180.0 / 180.0 / 180.0 / 180.0
E/Hartrees / -406.4368975 / -407.6124499 / -408.7256288 / -408.8274320 / -408.8341997 / -408.8816 841 / -408.9915753 / -408.9995204

Table S3: Observed and calculated wavenumbers for 3-fluorostyrene

B3LYP/6-311++G** / Ribeiro-Claro et al.a / This work
cis / trans / Raman liquid / Raman Liquid / INS Solid / IR Liquid
Calc. Freq. / IR int. / INS int. / Calc.Freq. / IR int. / INS int. / cis / trans / cis / trans / cis / trans / cis / trans
A’
n1 / 3224.5 / 10.8 / ~0.0 / 3225.4 / 10.9 / ~0.0 / 3100 / 3092.1 / 3092.1 / 3091.5 / 3091.5
n2 / 3205.4 / 1.8 / ~0.0 / 3205.3 / 1.6 / ~0.0 / 3084 / 3078.0 / 3078.0
n3 / 3203.3 / 1.01 / ~0.0 / 3194.2 / 7.3 / ~0.0 / 3071 / 3077.3 / 3077.3 / 3068.3 / 3068.3
n4 / 3185.3 / 13.6 / ~0.0 / 3187.5 / 2.9 / ~0.0 / 3050 / 3066.7 / 3066.7 / 3064.5 / 3064.5
n5 / 3169.0 / 5.7 / ~0.0 / 3174.3 / 6.3 / ~0.0 / 3040ir / 3040.7 / 3040.7 / 3040.4 / 3040.4
n6 / 3144.4 / 2.7 / ~0.0 / 3145.4 / 2.3 / ~0.0 / 3019 / 3013.6 / 3013.6 / 3011.9 / 3011.9
n7 / 3136.5 / 12.1 / ~0.0 / 3135.3 / 13.2 / ~0.0 / 2990 / 2987.6 / 2987.6 / 2984.0 / 2984.0
n8 / 1685.6 / 11.5 / ~0.0 / 1686.9 / 11.3 / ~0.0 / 1632 / 1637 / 1632.6 / 1645.2
n9 / 1648.1 / 38.3 / 0.03 / 1648.0 / 29.0 / 0.03 / 1614 / 1612.6 / 1612.6 / 1612.8 / 1612.8
n10 / 1618.7 / 60.8 / 0.02 / 1619.1 / 89.5 / 0.03 / 1583 / 1582.7 / 1582.7 / 1581.9 / 1581.9
n11 / 1514.4 / 30.3 / 0.06 / 1521.3 / 42.3 / 0.08 / 1490 / 1494 / 1484.0 / 1489.2 / 1479.7 / 1479.7 / 1484.5 / 1488.8
n12 / 1476.8 / 35.5 / 0.04 / 1475.1 / 6.0 / 0.02 / 1448 / 1445 / 1447.7 / 1447.7 / 1448.3 / 1448.3
n13 / 1455.2 / 20.1 / 0.02 / 1439.6 / 12.8 / 0.03 / 1416 / 1407 / 1414.9 / 1407.2 / 1414.6 / 1405.0
n14 / 1348.7 / 1.3 / 0.02 / 1349.1 / 0.6 / 0.01 / 1308 / 1308.6 / 1308.6
n15 / 1341.6 / 1.8 / 0.02 / 1340.5 / 1.2 / 0.04 / 1279 / 1278.3 / 1278.3
n16 / 1295.4 / 18.8 / 0.07 / 1306.6 / 5.4 / 0.09 / 1271 / 1270.3 / 1270.3 / 1299.8 / 1299.8 / 1269.9 / 1275.3
n17 / 1259.0 / 60.7 / 0.06 / 1267.6 / 98.5 / 0.06 / 1238 / 1255 / 1238.5 / 1253.8 / 1255.2 / 1255.2 / 1237.7 / 1254.1
n18 / 1185.2 / 1.1 / 0.1 / 1193.6 / 0.7 / 0.1 / 1163 / 1167 / 1162.3 / 1165.9 / 1206.1 / 1206.1 / 1162.0 / 1162.0
n19 / 1159.9 / 39.2 / 0.08 / 1156.1 / 29.0 / 0.1 / 1143 / 1139 / 1142.3 / 1139.0 / 1164.7 / 1153.1 / 1143.1 / 1139.1
n20 / 1097.4 / 3.8 / 0.1 / 1106.5 / 3.5 / 0.1 / 1080 / 1073 / 1071.7 / 1079.5 / 1086.1 / 1086.1 / 1070.8 / 1080.0
n21 / 1069.1 / 0.8 / 0.06 / 1043.6 / 4.2 / 0.07 / 1025ir / 1047.6 / 1047.6 / 1064.7 / 1064.7 / 1047.2 / 1024.5
n22 / 1014.9 / 0.3 / 0.08 / 1014.3 / 0.6 / 0.09 / 1002 / 1001.3 / 1001.3 / 1012.9 / 1012.9 / - / -
n23 / 933.8 / 37.7 / 0.1 / 936.3 / 47.3 / 0.2 / 920 / 916 / 911.4 / 918.4 / 935.2 / 935.2 / 918.5 / 918.5
n24 / 734.6 / 7.7 / 0.1 / 735.5 / 8.1 / 0.2 / 724 / 724.5 / 724.5 / 721.6 / 721.6 / 725.1 / 725.1
n25 / 561.4 / 3.2 / 0.1 / 585.4 / 5.1 / 0.2 / 518 / 524 / 556.8 / 556.8 / 553.9 / 559.5 / 554.4 / 578.5
n26 / 526.6 / 7.0 / 0.2 / 520.9 / 4.3 / 0.2 / 464 / 458 / 517.8 / 517.8 / 516.8 / 516.8
n27 / 465.2 / 0.9 / 0.2 / 471.1 / 1.6 / 0.3 / 455ir / 462.3 / 462.3 / 462.9 / 467.5 / 461.9 / 461.9
n28 / 406.2 / 2.2 / 0.2 / 369.6 / 0.2 / 0.2 / 404 / 372 / 403.4 / 370.1 / 406.6 / 371.7 / 403.5 / 403.5
n29 / 200.8 / 0.0 / 0.6 / 214.4 / 1.1 / 0.5 / 212 / 202.8 / 202.8
A’’
n30 / 1022.9 / 18.0 / 0.02 / 1024.8 / 17.9 / 0.02 / 995 / 989.9 / 989.9 / 983.0 / 983.0 / 988.4 / 988.4
n31 / 978.9 / 0.0 / 0.2 / 979.3 / 0.0 / 0.2 / - / 978.1 / 978.1 / 973.2 / 973.2 / - / -
n32 / 936.9 / 50.8 / 0.05 / 937.7 / 46.2 / 0.06 / 920 / 916 / 911.4 / 918.4 / 921.3 / 921.3 / 918.5 / 918.5
n33 / 904.5 / 0.1 / 0.2 / 900.5 / 1.4 / 0.2 / 872ir / 889.7 / 889.7
n34 / 884.9 / 18.0 / 0.1 / 889.2 / 26.1 / 0.2 / 835 / 880.9 / 880.9 / 872.2 / 872.2
n35 / 800.1 / 38.6 / 0.2 / 796.2 / 34.1 / 0.3 / 788 / 784 / 789.1 / 789.1 / 793.3 / 793.3 / 786.4 / 786.4
n36 / 730.9 / 12.2 / 0.2 / 733.2 / 9.3 / 0.2 / 715ir / 724.5 / 724.5 / 721.6 / 721.6 / 715.5 / 715.5
n37 / 664.0 / 11.9 / 0.2 / 665.0 / 14.6 / 0.3 / 656ir / 658.0 / 658.0 / 656.3 / 656.3 / 655.2 / 655.2
n38 / 536.8 / 0.3 / 0.3 / 526.9 / 0.5 / 0.3 / 557 / 522.0 / 522.0 / 529.6 / 529.6 / 522.1 / 522.1
n39 / 434.1 / 6.5 / 0.4 / 444.3 / 6.3 / 0.5 / 431ir / 431.7 / 438.1 / 431.5 / 431.5
n40 / 244.2 / 0.7 / 0.5 / 236.2 / 0.3 / 0.6 / 252 / 248 / 246.3 / 246.3 / 255.6 / 249.4
n41 / 194.7 / 1.1 / 0.5 / 202.7 / 1.9 / 0.6 / 216 / 210.6 / 216.6 / 219.1 / 219.1
n42 / 31.5 / 0.0 / 1.0 / 39.4 / 0.1 / 1.0 / (42) / (43) / - / -

a Ref. 14

This journal is © The Owner Societies 2002

Table S4: Diagonal Force Constants after the refinement of cis and trans-3-fluorostyrenea

cis / trans
Finitial / Ffinal / Finitial / Ffinal
A’
F1,1 / 5.965 / 6.225 / 5.837 / 6.069
F2,2 / 6.240 / 6.240 / 6.360 / 6.361
F3,3 / 6.302 / 5.785 / 6.163 / 5.725
F4,4 / 5.941 / 5.387 / 6.090 / 5.367
F5,5 / 6.152 / 4.937 / 6.031 / 4.657
F6,6 / 5.611 / 6.131 / 5.734 / 5.798
F7,7 / 5.153 / 6.004 / 5.146 / 5.292
F8,8 / 9.308 / 8.088 / 9.310 / 9.088
F9,9 / 5.529 / 5.243 / 5.591 / 5.181
F10,10 / 5.556 / 5.087 / 5.547 / 5.088
F11,11 / 5.623 / 5.148 / 5.623 / 5.189
F12,12 / 5.845 / 5.655 / 5.862 / 6.344
F13,13 / 5.633 / 5.188 / 5.573 / 5.159
F14,14 / 5.418 / 5.000 / 5.412 / 4.907
F15,15 / 5.589 / 5.134 / 5.588 / 5.159
F16,16 / 5.547 / 4.973 / 5.556 / 5.082
F17,17 / 1.366 / 1.166 / 1.367 / 1.528
F18,18 / 1.294 / 1.182 / 1.295 / 1.138
F19,19 / 1.329 / 1.399 / 1.328 / 1.385
F20,20 / 0.693 / 0.687 / 0.619 / 0.614
F21,21 / 1.013 / 1.056 / 0.754 / 0.707
F22,22 / 0.774 / 0.774 / 0.832 / 0.877
F23,23 / 0.910 / 0.860 / 1.261 / 1.404
F24,24 / 0.915 / 0.953 / 0.724 / 0.737
F25,25 / 0.547 / 0.482 / 0.591 / 0.531
F26,26 / 0.533 / 0.457 / 0.598 / 0.580
F27,27 / 0.496 / 0.489 / 0.518 / 0.487
F28,28 / 0.790 / 0.827 / 0.582 / 0.457
F29,29 / 0.555 / 0.503 / 0.734 / 0.682
A’’
F30,30 / 0.402 / 0.400 / 0.404 / 0.531
F31,31 / 0.276 / 0.241 / 0.275 / 0.254
F32,32 / 0.300 / 0.280 / 0.299 / 0.251
F33,33 / 0.270 / 0.299 / 0.270 / 0.232
F34,34 / 0.389 / 0.396 / 0.393 / 0.337
F35,35 / 0.262 / 0.273 / 0.264 / 0.267
F36,36 / 0.155 / 0.127 / 0.155 / 0.127
F37,37 / 0.396 / 0.403 / 0.154 / 0.154
F38,38 / 0.113 / 0.103 / 0.115 / 0.112
F39,39 / 0.268 / 0.386 / 0.388 / 0.315
F40,40 / 0.330 / 0.256 / 0.338 / 0.455
F41,41 / 0.185 / 0.185 / 0.309 / 0.421
F42,42 / 0.373 / 0.380 / 0.371 / 0.419

aUnits are consistent with energy measured in aJ, lengths in