Table 3.
Calculated vibrational frequencies (cm−1) assignments of 5TDOP (Experimental, theoretical by B3LYP/6-311++G(d,p) set).
| Mode no | Experimental wave number (cm−1) |
Theoretical wave number(cm−1) |
IIRc | I Raman |
Assignments (PED)a | |||
|---|---|---|---|---|---|---|---|---|
| FTIR | FT-RAMAN | Unscaled | Scaledb | Relative | Absoluted | |||
| 102 | - | - | 3206 | 3081 | 0 | 555 | 13 | γCH(88) |
| 101 | - | - | 3204 | 3079 | 1 | 50 | 1 | γCH(90) |
| 100 | - | 3075(w) | 3197 | 3073 | 4 | 704 | 16 | γCH(88) |
| 99 | - | - | 3191 | 3067 | 1 | 129 | 3 | γCH(96) |
| 98 | - | - | 3188 | 3064 | 8 | 340 | 8 | γCH(87) |
| 97 | - | 3047(w) | 3175 | 3051 | 4 | 251 | 6 | γCH(86) |
| 96 | - | - | 3165 | 3041 | 1 | 110 | 3 | γCH(91) |
| 95 | - | 2965(s) | 3092 | 2971 | 10 | 258 | 6 | γCH(100) |
| 94 | 2939(m) | 2947(s) | 3057 | 2938 | 16 | 439 | 10 | γCH(92) |
| 93 | - | - | 3051 | 2932 | 18 | 385 | 9 | γCH(95) |
| 92 | - | - | 3039 | 2921 | 20 | 214 | 5 | γCH(91) |
| 91 | 2914(m) | 2911(s) | 3034 | 2916 | 1 | 67 | 2 | γCH(94) |
| 90 | - | - | 2999 | 2882 | 4 | 392 | 9 | γCH(91) |
| 89 | - | - | 2946 | 2831 | 33 | 393 | 9 | γCH(95) |
| 88 | - | - | 2904 | 2791 | 61 | 751 | 18 | γCH(90) |
| 87 | - | 2774(w) | 2891 | 2778 | 25 | 153 | 4 | γCH(92) |
| 86 | - | - | 1646 | 1582 | 3 | 262 | 6 | γCC(59) |
| 85 | 1577(m) | - | 1634 | 1570 | 1 | 494 | 12 | γCC(55) |
| 84 | - | - | 1612 | 1549 | 4 | 458 | 11 | γCC(45) |
| 83 | 1538(m) | - | 1607 | 1544 | 1 | 92 | 2 | γCC(51) |
| 82 | - | - | 1530 | 1470 | 4 | 116 | 3 | βHCH(81) |
| 81 | 1461(s) | 1458(s) | 1517 | 1458 | 6 | 62 | 1 | βHCH(55) |
| 80 | - | - | 1515 | 1456 | 2 | 29 | 1 | βHCH(72) |
| 79 | - | - | 1507 | 1448 | 91 | 59 | 1 | βHCC(16) |
| 78 | - | - | 1501 | 1443 | 5 | 99 | 2 | βHCH(76)+τHCCC(10) |
| 77 | 1424(s) | - | 1490 | 1432 | 9 | 137 | 3 | βHCH(83) |
| 76 | - | 1423(m) | 1472 | 1415 | 23 | 14 | 0 | βHCC(52) |
| 75 | - | - | 1457 | 1400 | 1 | 60 | 1 | βHCN(82) |
| 74 | - | 1387(s) | 1433 | 1377 | 13 | 32 | 1 | γCC(23)+βHCC(11) |
| 73 | - | 1358(s) | 1404 | 1349 | 6 | 126 | 3 | βHCC(50) |
| 72 | - | 1320(m) | 1384 | 1330 | 7 | 101 | 2 | βHCC(62) |
| 71 | - | - | 1362 | 1309 | 9 | 279 | 7 | τHCCC(29) |
| 70 | - | 1285(m) | 1343 | 1290 | 2 | 108 | 3 | βHCC(37) |
| 69 | 1280(m) | - | 1331 | 1279 | 1 | 192 | 4 | βHCC(38)+γCC(23) |
| 68 | - | - | 1321 | 1270 | 16 | 182 | 4 | βHCC(16)+γCC(49) |
| 67 | 1258(m) | 1259(m) | 1309 | 1258 | 3 | 56 | 1 | γCC(32) |
| 66 | - | - | 1305 | 1254 | 7 | 23 | 1 | βHCC(45) |
| 65 | - | - | 1289 | 1239 | 1 | 37 | 1 | βHCC(44) |
| 64 | - | 1232(m) | 1279 | 1229 | 14 | 156 | 4 | βHCC(45) |
| 63 | - | 1212(m) | 1263 | 1214 | 100 | 298 | 7 | γCC(56) |
| 62 | 1201(m) | - | 1253 | 1204 | 28 | 158 | 4 | γCC(19)+τHCCC(37) |
| 61 | - | - | 1233 | 1185 | 9 | 349 | 8 | γCC(36)+βHCC(14) |
| 60 | - | - | 1231 | 1183 | 4 | 140 | 3 | βHCN(69) |
| 59 | - | - | 1219 | 1172 | 11 | 1004 | 24 | γCC(42) |
| 58 | - | - | 1211 | 1163 | 43 | 49 | 1 | γCC(30) |
| 57 | - | - | 1196 | 1150 | 2 | 44 | 1 | βHCC(37) |
| 56 | - | - | 1186 | 1139 | 14 | 82 | 2 | βHCC(27) |
| 55 | - | 1127(vs) | 1181 | 1135 | 2 | 98 | 2 | βHCC(68) |
| 54 | - | - | 1149 | 1105 | 6 | 151 | 4 | βHCN(18) |
| 53 | 1082(s) | 1083(m) | 1131 | 1087 | 10 | 40 | 1 | βHCN(51) |
| 52 | - | - | 1128 | 1084 | 7 | 64 | 1 | βHCC(44) |
| 51 | - | - | 1103 | 1060 | 18 | 536 | 13 | βHCC(38) |
| 50 | - | - | 1091 | 1048 | 7 | 71 | 2 | γCC(40) |
| 49 | - | 1034(s) | 1072 | 1030 | 6 | 37 | 1 | γCC(28) |
| 48 | 1019(s) | - | 1066 | 1025 | 0 | 816 | 19 | γCC(51) |
| 47 | - | - | 1051 | 1010 | 2 | 430 | 10 | γCC(23)+τHCCC(19) |
| 46 | - | - | 1043 | 1002 | 4 | 70 | 2 | γCC(37)+τHCCC(11) |
| 45 | 952(m) | - | 988 | 949 | 0 | 3 | 0 | τHCCH(89) |
| 44 | - | 934(m) | 984 | 945 | 0 | 29 | 1 | γCC(10)+τHCCC(23) |
| 43 | 929(m) | - | 961 | 923 | 1 | 6 | 0 | τHCCC(78) |
| 42 | - | - | 958 | 921 | 1 | 40 | 1 | τHCCC(76)+βHCC(10)+γCC(11) |
| 41 | - | - | 958 | 920 | 10 | 6 | 0 | γCC(11)+γCC(15) |
| 40 | 879(s) | 876(vs) | 922 | 886 | 2 | 153 | 4 | βHCC(43) |
| 39 | - | - | 894 | 859 | 4 | 39 | 1 | βHCC(10)+τHCNC(35) |
| 38 | - | - | 877 | 843 | 4 | 43 | 1 | γNC(15)+τHCCCl(56) |
| 37 | - | - | 875 | 841 | 7 | 142 | 3 | γNC(14)+τHCCCl(11) |
| 36 | - | 824(w) | 869 | 835 | 8 | 146 | 3 | γNC(61) |
| 35 | - | - | 846 | 813 | 11 | 13 | 0 | γCC(11)+τHCCC(46) |
| 34 | - | 783(m) | 820 | 788 | 2 | 51 | 1 | γCC(23)+τHCCC(15) |
| 33 | - | 749(m) | 775 | 745 | 9 | 25 | 1 | βHCC(15)+τHCCC(11) |
| 32 | - | - | 767 | 737 | 19 | 211 | 5 | τHCCC(48) |
| 31 | - | 713(w) | 758 | 729 | 7 | 148 | 3 | τHCCC(64) |
| 30 | 704(s) | - | 721 | 692 | 1 | 759 | 18 | γCC(22)+τHCNC(16)+τHCCC(13) |
| 29 | - | 648(m) | 675 | 648 | 8 | 101 | 2 | γClC(43) |
| 28 | 630(s) | - | 654 | 629 | 0 | 180 | 4 | βHCC(47) |
| 27 | - | - | 638 | 613 | 2 | 91 | 2 | βHCC(50) |
| 26 | - | - | 621 | 597 | 1 | 62 | 1 | βHCC(49) |
| 25 | - | 565(w) | 599 | 576 | 4 | 86 | 2 | βCCC(43) |
| 24 | 588(s) | - | 580 | 558 | 1 | 129 | 3 | βHCC(15)+τHCCC(19) |
| 23 | - | 517(m) | 552 | 530 | 0 | 72 | 2 | βHCC(10)+τHCCC(34) |
| 22 | - | - | 518 | 498 | 2 | 88 | 2 | τHCNC(40) |
| 21 | - | 474(s) | 490 | 471 | 2 | 127 | 3 | βCCC(37) |
| 20 | - | - | 475 | 456 | 4 | 123 | 3 | τHCCC(12)+γClC(18) |
| 19 | - | 417(w) | 442 | 425 | 1 | 81 | 2 | τHCCC(53) |
| 18 | - | - | 410 | 394 | 1 | 244 | 6 | τHCNC(35)+τHCNC(10) |
| 17 | - | 367(m) | 392 | 377 | 2 | 73 | 2 | τHCCCl(36) |
| 16 | - | 343(m) | 368 | 354 | 0 | 124 | 3 | τHCNC(30) |
| 15 | - | - | 342 | 328 | 1 | 770 | 18 | βHCC(21) |
| 14 | - | - | 331 | 319 | 0 | 180 | 4 | τHCNC(26) |
| 13 | - | - | 324 | 312 | 2 | 1026 | 24 | τHCNC(48) |
| 12 | - | 289(m) | 289 | 278 | 0 | 280 | 7 | τHCNC(27)+βHCC(10) |
| 11 | - | - | 275 | 264 | 2 | 356 | 8 | βHCC(23) |
| 10 | - | 243(m) | 247 | 237 | 0 | 250 | 6 | τHCNC(65) |
| 9 | - | - | 236 | 227 | 0 | 886 | 21 | τHCNC(40) |
| 8 | - | 195(m) | 209 | 201 | 0 | 608 | 14 | τHCCC(26) |
| 7 | - | - | 170 | 163 | 0 | 267 | 6 | τHCCC(42) |
| 6 | - | 127(s) | 147 | 142 | 0 | 1331 | 31 | τHCNC(13) |
| 5 | - | - | 113 | 109 | 0 | 4267 | 100 | τHCCC(57) |
| 4 | - | - | 97 | 93 | 0 | 2487 | 58 | τHCCC(68) |
| 3 | - | - | 77 | 74 | 0 | 3696 | 87 | τHCCC(62) |
| 2 | - | - | 58 | 56 | 0 | 4022 | 94 | τHCCC(57) |
| 1 | - | - | 36 | 35 | 0 | 4150 | 97 | βCOC(28)+τHCNC(14) |
a
γ-stretching,γa-Symmetrical stretching,γas-asymmetrical stretching, β-inplane bending,ω-outplane bending, τ-torsion, vs-very strong, s-strong, m-medium, w-weak.
b
Scaling factor: 0.961 for B3LYP/6-311+G(d,p).
c
Relative absorption intensities normalized with highest peak absorption equal to 100.
d
Relative Raman intensities normalized to 100.