supplementary.doc 125KB Jun 05 2011 09:30:52 PM

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SUPPLEMENTARY MATERIAL

TABLE SI.

Unscaled B3LYP/6-311G(d,p) harmonic vibrational frequencies (cm

-1

_{) of the various}

intermediates and transition states on the doublet C

4

H

3

PES and the C(

3

P

j

) + C

3

H

3

(X

2

B

1

) reaction

products.

Species

Frequencies (cm

–1

₎

i1 230, 345, 448, 696, 713, 763, 902, 927, 1013, 1419, 1622, 1808, 3133, 3215, 3292 i2 71, 129, 374, 452, 666, 884, 903, 960, 975, 1407, 1477, 1881, 2919, 3061, 3129 i3a (B3LYP) 82, 229, 264, 378, 541, 637, 885, 901, 977, 1433, 1800, 2016, 3064, 3124, 3468 i4 224, 330, 534, 851, 878, 967, 1015, 1074, 1295, 1378, 1468, 1657, 3135, 3152, 3243 i5-cis 224, 328, 533, 649, 675, 686, 799, 834, 1011, 1264, 1639, 2209, 3024, 3246, 3477 i5-trans 213, 339, 511, 647, 683, 705, 852, 872, 992, 1266, 1623, 2199, 3096, 3240, 3477 i6 70, 154, 319, 349, 794, 991, 1019, 1366, 1398, 1440, 1465, 1988, 2998, 3057, 3065 i7 171, 262, 355, 703, 899, 934, 1030, 1041, 1087, 1243, 1492, 1684, 3101, 3201, 3286 i8 33, 311, 390, 640, 786, 1018, 1036, 1331, 1395, 1457, 1467, 1714, 3033, 3099, 3113 i9 357, 385, 494, 655, 708, 789, 871, 885, 1011, 1043, 1602, 1801, 3223, 3268, 3291 i10 309, 582, 609, 658, 791, 830, 837, 1020, 1086, 1165, 1476, 1598, 3148, 3261, 3274 i11 418, 659, 738, 800, 909, 1017, 1041, 1083, 1165, 1186, 1446, 1512, 3088, 3099, 3172 i12 502, 669, 766, 868, 923, 1031, 1054, 1100, 1122, 1178, 1467, 1496, 3105, 3170, 3285 p1 237, 237, 525, 525, 662, 662, 670, 670, 917, 2111, 2285, 3477, 3479

p2 159, 206, 418, 518, 783, 925, 950, 1374, 1746, 2164, 3134, 3214 p3a _{541, 555, 615, 802, 924, 1033, 1040, 1246, 1285, 1411, 3210, 3227}

p4 435, 492, 951, 964, 1009, 1052, 1114, 1229, 1493, 1528, 3100, 3179 p5 179, 375, 666, 728, 819, 830, 971, 986, 1650, 1866, 3278, 3333 HCCCC 284, 284, 660, 660, 927, 1027, 1027, 2121, 2278, 3476

tsi1i2a _{345i, 335, 384, 528, 689, 790, 980, 1068, 1142, 1406, 1659, 1874, 3155, 3263, 3388}

tsi1i3 735i, 116, 312, 502, 572, 844, 882, 964, 1044, 1420, 1636, 1765, 3031, 3158, 3396 tsi1i11 474i, 346, 540, 738, 814, 910, 928, 953, 1072, 1297, 1474, 1535, 3103, 3197, 3222 tsi1i12 300i, 419, 576, 644, 822, 935, 979, 1029, 1127, 1382, 1480, 1601, 3096, 3181, 3262 tsi2i3 154i, 116, 289, 404, 552, 822, 915, 919, 974, 1425, 1580, 1876, 2685, 3058, 3132 tsi2i4 1042i, 82, 228, 271, 427, 493, 816, 863, 954, 1403, 1616, 1909, 2422, 3105, 3181 tsi2i5 1896i, 86, 428, 476, 742, 771, 830, 1011, 1081, 1154, 1499, 1628, 1680, 3211, 3285 tsi3i4 1007i, 321, 444, 512, 683, 701, 822, 1008, 1103, 1437, 1529, 1755, 1957, 3132, 3233 tsi3i5 2124i, 192, 216, 309, 482, 552, 587, 675, 817, 893, 1842, 2153, 2322, 3061, 3474 tsi3i6 1528i, 414, 453, 468, 703, 946, 1004, 1070, 1071, 1323, 1474, 1526, 1752, 3077, 3168 tsi4i6 1442i, 186, 201, 419, 626, 895, 951, 1050, 1211, 1473, 1550, 1969, 2161, 3052, 3179 tsi4i7 569i, 231, 314, 662, 782, 976, 997, 1031, 1227, 1289, 1491, 1792, 3082, 3206, 3225 tsi5i9 725i, 337, 375, 496, 510, 595, 755, 866, 947, 1156, 1659, 1889, 3152, 3240, 3415 tsi5i10 678i, 413, 524, 546, 694, 826, 872, 909, 1028, 1203, 1597, 1678, 3125, 3199, 3351 tsi6i8 1072i, 51, 215, 309, 864, 999, 1032, 1376, 1444, 1446, 1460, 1624, 2985, 3064, 3083 tsi7i11 160i, 256, 707, 777, 842, 906, 1036, 1056, 1102, 1192, 1485, 1873, 3072, 3148, 3221 tsi8i11a _{851i, 459, 498, 688, 918, 965, 1080, 1120, 1258, 1488, 1652, 1830, 2604, 3135, 3244}

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tsi4p2 560i, 178, 183, 215, 368, 450, 520, 795, 916, 948, 1382, 1734, 2136, 3135, 3228 tsi6p2 208i, 144, 158, 224, 273, 420, 516, 788, 922, 953, 1375, 1730, 2147, 3135, 3216 tsi7p5 449i, 149, 178, 275, 385, 670, 729, 805, 832, 966, 992, 1563, 1846, 3281, 3333 tsabstra _{909i, 161, 233, 305, 451, 452, 596, 637, 902, 925, 1025, 2203, 2917, 3615, 3690}

tsi3(1,4)pr1 1297i, 361, 404, 471, 562, 598, 654, 806, 1089, 1190, 1209, 1743, 1813, 1992, 3403 tsi6(1,1)pr1 1351i, 98, 170, 196, 371, 510, 586, 756, 938, 994, 1262, 1732, 2073, 3133, 3338 n-C4H3(2A”)a 119, 218, 437,542, 866, 894, 921, 935, 1094, 1345, 1529, 2253, 3118, 3167, 3269

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H(5) -2.019 0.298 0.167

H(6) -0.009 -0.951 -0.144

H(7) 0.906 -1.079 -0.208

tsi3(1,1)pr1 (2_A”)

C(1) 0.356 -0.350 0.152

C(2) -0.935 -0.381 0.203

C(3) 1.623 -0.115 0.048

C(4) -2.197 -0.674 0.308

H(6) 3.117 0.674 -0.205

H(7) -3.117 0.048 0.331

H(5) 2.661 -0.300 -0.331

tsi6(1,1)pr1

C(1) -2.361 -0.327 0.223

C(2) -1.087 -0.398 0.070

C(3) 0.198 -0.493 -0.088

C(4) 1.473 -0.409 -0.206

H(5) 2.361 -0.968 -0.422

H(6) 1.963 0.968 -0.395

H(7) 2.050 0.792 0.422

tsabstr

C(1) -1.929 -0.927 -0.358

C(2) -0.715 -0.840 -0.360

C(3) 0.624 -0.718 -0.348

C(4) 1.872 -0.866 -0.478

H(5) -2.989 -1.008 -0.358

H(6) 2.884 0.319 0.115