TABLE II.
Spectroscopic constants for isotopologues of thiophene (S-reduced Hamiltonian, Ir representation).a
| Isotopologue | C4H4Sb | [2-13C]b | [3-13C]b | [34S]b | [33S]b | [2-2H]b |
|---|---|---|---|---|---|---|
| A0(S) (MHz) | 8 041.595 658(44) | 7 852.775 54(31) | 7 981.280 38(34) | 8 041.715 07(20) | 8 041.651 5(20) | 7 437.197 29(20) |
| B0(S) (MHz) | 5 418.262 629(36) | 5 418.405 62(10) | 5 319.305 933(98) | 5 274.184 579(69) | 5 344.297 61(59) | 5 413.721 571(84) |
| C0(S) (MHz) | 3 235.780 781 (39) | 3 204.806 550(87) | 3 190.618 898(88) | 3 183.843 198(67) | 3 209.258 34(13) | 3 131.815 069(83) |
| DJ (kHz) | 0.703 074(26) | 0.699 151(61) | 0.675 952(59) | 0.680 947(46) | 0.691 62(14) | 0.681 599(56) |
| DJK (kHz) | 0.535 835(27) | 0.506 44(37) | 0.551 34(32) | 0.510 05(19) | 0.521 62(77) | 0.444 81(26) |
| DK (kHz) | 1.652 637(67) | 1.583 22(56) | 1.611 09(65) | 1.699 58(45) | 1.665 9(33) | 1.269 81(35) |
| d1 (kHz) | −0.3116416(36) | −0.313 237(19) | −0.298 436(19) | −0.297 537(19) | −0.304 257(86) | −0.313 542(24) |
| d2 (kHz) | −0.067 394 2(18) | −0.068 193(11) | −0.064 8635(97) | −0.062 968 7(79) | −0.065 028(28) | −0.069 745 1(78) |
| HJ (Hz) | 0.000 212 5(54) | 0.000 218(14) | 0.000 203(14) | 0.000 197(12) | [0.000 212] | 0.000 225(17) |
| HJK (Hz) | −0.001668(10) | −0.001 54(18) | −0.001 48(15) | [–0.001 66] | [–0.001 69] | −0.001 82(18) |
| HKJ (Hz) | 0.002 158(32) | 0.003 03(51) | 0.001 79(36) | 0.002 09(20) | [0.002 18] | 0.00247(37) |
| HK (Hz) | [0.000 672] | [0.000 597] | [0.000 672] | [0.000 759] | [0.000 716] | [0.000 387] |
| h1 (Hz) | 0.000 131 05(73) | [0.000 128] | [0.000 121] | 0.000 122 0(61) | [0.000 126] | 0.000 122 4(73) |
| h2 (Hz) | 0.000 043 05(56) | [0.000 0360] | [0.000 038 6] | 0.000 041 4(25) | [0.000 036 7] | 0.000 032 9(50) |
| h3 (Hz) | 0.000 022 52(14) | [0.000 0221] | [0.000 020 3] | 0.000 021 08(86) | [0.000 020 5] | 0.000 021 9(10) |
| Nlinesc | 3 270 | 965 | 983 | 1262 | 258 | 1350 |
| σ (MHz) | 0.022 | 0.030 | 0.029 | 0.024 | 0.029 | 0.028 |
| κd | −0.917 | −0.047 5 | −0.111 | −0.139 | −0.116 | 0.060 0 |
| Δi (μÅ2)e | 0.065 692 3(20) | 0.066 543 0(53) | 0.066 298 4(55) | 0.066 441 0(39) | 0.065 992(20) | 0.064 984 2(49) |
| Isotopologue | [3-2H]b | [2,3-2H] | [2,4-2H] | [2,5-2H] | [3,4-2H] | [2,3,4-2H] |
|---|---|---|---|---|---|---|
| A0(S) (MHz) | 7 855.997 58(11) | 7 277.001 30(27) | 7 288.383 17(21) | 6 903.426 58(12) | 7 616.557(16) | 7 072.276 05(33) |
| B0(S) (MHz) | 5 138.229 854(63) | 5 137.627 501(97) | 5 124.657 587(77) | 5 410.698 544 (68) | 4 914.679 4 (78) | 4 909.469 19 (10) |
| C0(S) (MHz) | 3 105.222 733 (72) | 3 010.350 104 (87) | 3 007.831 223 (83) | 3 032.130 273 (70) | 2 986.054 60 (18) | 2 896.801 160 (94) |
| DJ (kHz) | 0.606 648 (43) | 0.592 435 (59) | 0.578 844 (46) | 0.666 346 (46) | 0.537 95 (23) | 0.520 247 (60) |
| DJK (kHz) | 0.567 38 (10) | 0.457 48 (34) | 0.538 407 (90) | 0.326 19 (15) | [0.531] | 0.469 51 (35) |
| DK (kHz) | 1.524 38 (13) | 1.178 63 (53) | 1.142 75 (32) | 1.001 64 (15) | [1.40] | 1.075 91 (53) |
| d1 (kHz) | −0.265 109 (10) | −0.268 999 (28) | −0.262 829 (14) | −0.316 194 (18) | −0.233 02 (18) | −0.234 458 (26) |
| d2 (kHz) | −0.058 206 4 (36) | −0.060 220 (10) | −0.060 718 8 (32) | −0.070 902 5 (42) | −0.050 945 (68) | −0.053 293 1 (94) |
| HJ (Hz) | 0.000 146 5 (92) | 0.000 142 (21) | 0.000 120 9 (96) | 0.000 236 (10) | [0.000 123] | 0.000 123 (19) |
| HJK (Hz) | −0.001 063 (43) | −0.001 10 (18) | [–0.000 752] | −0.001 619 (44) | [–0.000 972] | −0.000 80 (11) |
| HKJ (Hz) | 0.001 17 (10) | 0.001 43 (38) | [0.000 762] | 0.002 274 (91) | [0.001 29] | 0.001 23 (28) |
| HK (Hz) | [0.000 920] | [0.000 530] | [0.000 791] | [0.000 116] | [0.000 696] | [0.000 472] |
| h1 (Hz) | 0.0000964 (20) | 0.000 084 (10) | [0.000 087 8] | 0.000 122 2 (46) | [0.000 079 4] | 0.000 082 1 (97) |
| h2 (Hz) | 0.000 038 5 (12) | 0.000 030 7 (52) | [0.000 040 1] | [0.000 030 9] | [0.000 029 3] | [0.000 029 2] |
| h3 (Hz) | 0.000 016 76 (26) | 0.000 018 1 (12) | [0.000 016 8] | 0.000 025 05 (58) | [0.000 013 6] | 0.000 015 9 (14) |
| Nlinesc | 1 880 | 1 187 | 1 171 | 1 651 | 203 | 1 049 |
| σ (MHz) | 0.029 | 0.030 | 0.030 | 0.027 | 0.038 | 0.032 |
| κd | −0.144 1 | −0.002 8 | −0.011 0 | 0.228 8 | −0.167 0 | −0.036 0 |
| Δi (μÅ2)e | 0.064 312 3 (41) | 0.063 507 3 (58) | 0.063 593 3 (53) | 0.063 937 3 (43) | 0.063 22 (22) | 0.062 244 6 (70) |
| Isotopologue | [2,3,5-2H] | [2,3,4,5-2H] | [2,5-2H, 34S] | [2,3,5-2H, 34S] | [2,3,4,5-2H, 34S]f | [2,5-2H, 2-13C] |
|---|---|---|---|---|---|---|
| A0(S) (MHz) | 6 775.849 57 (12) | 6 587.731 79 (20) | 6 903.535 0 (11) | 6 773.399 56 (92) | 6 588.36 (32) | 6 763.947 (25) |
| B0(S) (MHz) | 5 124.449 058 (64) | 4 905.808 107 (85) | 5 268.343 08 (37) | 4 992.253 90 (32) | 4 777.72 (18) | 5 410.781 (17) |
| C0(S) (MHz) | 2 916.731 610 (66) | 2 810.897 843 (77) | 2 986.906 70 (30) | 2 872.969 11 (23) | 2 768.492 1 (18) | 3 004.929 39 (26) |
| DJ (kHz) | 0.567 721 (40) | 0.507 404 (48) | 0.645 38 (15) | 0.552 89 (13) | 0.487 0 (65) | 0.667 44 (43) |
| DJK (kHz) | 0.418 49 (19) | 0.377 71 (25) | 0.317 68 (78) | 0.376 2 (24) | [0.348] | [0.271] |
| DK (kHz) | 0.888 63 (18) | 0.843 81 (29) | 1.035 4 (14) | 0.964 8 (52) | [0.882] | [0.996] |
| d1 (kHz) | −0.266 630 (16) | −0.236 303 (23) | −0.302 494 (66) | −0.255 757 (61) | −0.222 5 (45) | −0.318 45 (33) |
| d2 (kHz) | −0.062 119 2 (50) | −0.054 507 4 (35) | −0.066 729 (35) | −0.057 659 (83) | −0.050 3 (12) | −0.070 65 (11) |
| HJ (Hz) | 0.000 151 (12) | 0.000 144 (17) | 0.000 237 (30) | 0.000 111 (16) | [0.000 116] | [0.000 229] |
| HJK (Hz) | −0.000 862 (70) | −0.000 906 (94) | −0.001 27 (36) | [–0.000 792] | [–0.000 780] | [–0.001 54] |
| HKJ (Hz) | [0.000 857] | [0.001 05] | [0.001 85] | [0.000 895] | [0.001 01] | [0.002 03] |
| HK (Hz) | [0.000 474] | [0.000 270] | [0.000 173] | [0.000 473] | [0.000 301] | [0.000 068 2] |
| h1 (Hz) | 0.000 093 6 (52) | 0.000 080 2 (86) | [0.000 116] | [0.000 084 3] | [0.000 071 7] | [0.000 121] |
| h2 (Hz) | 0.000 037 9 (16) | [0.000 027 0] | [0.000 029 2] | [0.000 032 8] | [0.000 024 9] | [0.000 027 3] |
| h3 (Hz) | 0.000 017 90 (55) | 0.000 015 52 (66) | [0.000 021 0] | [0.000 015 8] | [0.000 013 1] | [0.000 023 6] |
| Nlinesc | 1672 | 1 349 | 420 | 458 | 39 | 165 |
| σ (MHz) | 0.027 | 0.031 | 0.042 | 0.039 | 0.039 | 0.044 |
| κd | 0.144 2 | 0.109 3 | 0.165 0 | 0.086 7 | 0.052 0 | 0.280 0 |
| Δi (μÅ2)e | 0.062 470 0 (44) | 0.061 092 5 (58) | 0.064 788 (22) | 0.063 317 (19) | 0.060 8 (56) | 0.064 52 (41) |
| Isotopologue | [2,5-2H, 3-13C] | [2-2H, 34S] | [3-2H, 2-13C] | [3-2H, 3-13C] | [3-2H, 4-13C] | [3-2H, 5-13C] |
|---|---|---|---|---|---|---|
| A0(S) (MHz) | 6 860.081 (23) | 7 436.863 (16) | 7 681.747 (50) | 7 816.981 (61) | 7 775.956 (56) | 7 671.947 (41) |
| B0(S) (MHz) | 5 310.447 (15) | 5 270.700 0 (92) | 5 137.725 (24) | 5 045.949 (27) | 5 060.889 (25) | 5 138.103 (19) |
| C0(S) (MHz) | 2 992.158 23 (26) | 3 083.341 37 (19) | 3 077.431 02 (28) | 3 065.287 40(28) | 3 064.440 94 (27) | 3 075.993 25 (24) |
| DJ (kHz) | 0.641 97 (37) | 0.663 89 (23) | 0.605 49 (44) | 0.585 84(48) | 0.588 84 (51) | 0.602 06 (37) |
| DJK (kHz) | [0.329] | [0.404] | [0.520] | [0.563] | [0.552] | [0.534] |
| DK (kHz) | [0.989] | [1.33] | [1.47] | [1.51] | [1.49] | [1.46] |
| d1 (kHz) | −0.303 29 (28) | −0.301 28 (18) | −0.267 33 (34) | −0.254 28 (37) | −0.256 68 (39) | −0.265 54 (28) |
| d2 (kHz) | −0.067 76 (10) | −0.065 200 (70) | −0.058 59 (13) | −0.055 59 (14) | −0.056 13 (14) | −0.058 44 (11) |
| HJ (Hz) | [0.000 200] | [0.000 203] | [0.000 151] | [0.000 134] | [0.000 144] | [0.000 147] |
| HJK (Hz) | [–0.001 31] | [–0.001 48] | [–0.001 14] | [–0.000 949] | [–0.001 09] | [–0.001 08] |
| HKJ (Hz) | [0.001 71] | [0.001 89] | [0.001 39] | [0.001 05] | [0.001 39] | [0.001 24] |
| HK (Hz) | [0.000 166] | [0.000 450] | [0.000 827] | [0.000 979] | [0.000 771] | [0.000 901] |
| h1 (Hz) | [0.000 114] | [0.000 119] | [0.000 095 9] | [0.000 090 4] | [0.000 0931] | [0.000 095 3] |
| h2 (Hz) | [0.000 032 9] | [0.000 034 0] | [0.000 034 6] | [0.000 036 8] | [0.000 0346] | [0.000 036 0] |
| h3 (Hz) | [0.000 021 6] | [0.000 020 3] | [0.000 016 9] | [0.000 015 5] | [0.000 0159] | [0.000 016 8] |
| Nlinesc | 174 | 237 | 133 | 112 | 113 | 143 |
| σ (MHz) | 0.045 | 0.039 | 0.046 | 0.041 | 0.041 | 0.040 |
| κd | 0.198 7 | 0.004 9 | −0.105 1 | −0.166 3 | −0.152 5 | −0.102 6 |
| Δi (μÅ2)e | 0.064 70 (38) | 0.065 73 (23) | 0.065 19 (64) | 0.064 83 (75) | 0.064 95 (69) | 0.065 15 (52) |
| Isotopologue | [3-2H, 34S] | [3-2H, 33S]f | ||||
|---|---|---|---|---|---|---|
| A0(S) (MHz) | 7 854.541 26 (65) | 7 854.84 (47) | ||||
| B0(S) (MHz) | 5 003.229 49 (16) | 5 069.12 (20) | ||||
| C0(S) (MHz) | 3 055.165 94 (14) | 3079.662 92 (44) | ||||
| DJ (kHz) | 0.588 513 (76) | 0.595 8 (15) | ||||
| DJK (kHz) | 0.537 56 (46) | [0.534] | ||||
| DK (kHz) | 1.570 5 (12) | [1.56] | ||||
| d1 (kHz) | −0.253 387 (27) | −0.257 1 (11) | ||||
| d2 (kHz) | −0.054 331 (10) | −0.054 93 (42) | ||||
| HJ (Hz) | 0.000 157 (17) | [0.000 146] | ||||
| HJK (Hz) | −0.001 03 (16) | [–0.001 103] | ||||
| HKJ (Hz) | [0.001 26] | [0.001 28] | ||||
| HK (Hz) | [0.000 964] | [0.000 942] | ||||
| h1 (Hz) | [0.000 092 2] | [0.000 094 3] | ||||
| h2 (Hz) | [0.000 033 0] | [0.000 034 5] | ||||
| h3 (Hz) | [0.000 015 0] | [0.000 015 7] | ||||
| Nlinesc | 664 | 57 | ||||
| σ (MHz) | 0.035 | 0.045 | ||||
| κd | −0.188 2 | −0.166 7 | ||||
| Δi (μÅ2)e | 0.065 030 5 (99) | 0.064 8 (56) |
a
Values in square brackets held fixed at the CCSD(T)/cc-pCVTZ predicted value in the least-squares fit.
b
Includes previously reported transitions.24,25,31,32,34
c
Number of independent frequencies in the fit.
d
κ = (2B − A − C)/(A − C), calculated using PLAN.
e
Δi = Ic − Ib − Ia, calculated using PLAN.
f
Shaded columns indicate that the isotopologue is not included in structure determination.