Table 1. Rotational Parameters for the Two Isomers of the Thiophenol Dimer.
| experiment |
theorya |
||||||
|---|---|---|---|---|---|---|---|
| Isomer I | Isomer IIb |
|
|||||
| v = 0 | v = 1 | PD1-trans | PD1-cis | PD2-cis | PD2-trans | ||
| A,c MHz | 662.748 50(27)d | 626.720 05(70) | 626.719 15(70) | 693.6 | 690.4 | 628.4 | 629.7 |
| B, MHz | 499.492 41(20) | 511.484 22(83) | 511.482 95(83) | 496.3 | 496.9 | 527.6 | 530.3 |
| C, MHz | 338.596 68(19) | 422.945 94(94) | 422.903 05(91) | 347.3 | 348.9 | 435.8 | 435.6 |
| κ | –0.01 | –0.13 | –0.14 | –0.13 | –0.05 | –0.02 | |
| ΔJ, kHz | 0.1611(13) | 0.1884(99) | 0.355 | 0.329 | 0.077 | 0.094 | |
| ΔJK, kHz | 28.7175(37) | 0.090(41) | –0.527 | –0.402 | 0.297 | 0.225 | |
| ΔK, kHz | –28.7008(36) | –0.199(38) | 0.217 | 0.121 | –0.312 | –0.253 | |
| δJ, kHz | 0.051 85(50) | –0.0276(47) | 0.041 | 0.030 | –0.024 | –0.022 | |
| δK, kHz | 14.1665(20) | 0.330(28) | 0.054 | 0.150 | 0.495 | 0.446 | |
| ΔE10, MHz | 8.8698(51) | ||||||
| Ne | 145 | 139 | |||||
| σ, kHz | 7.6 | 19.8 | |||||
| |μa|, Debyef | not detected | not detected | 0.1 | 0.5 | 0.0 | 0.8 | |
| |μb|, Debye | detected | detected | 1.5 | 2.1 | 1.6 | 1.1 | |
| |μc|, Debye | not detected | detected | 0.4 | 0.9 | 1.1 | 0.2 | |
| ΔE,g kJ mol–1 | 0.85 | 1.56 | 0.00 | 0.42 | |||
| ΔG100 K, kJ mol–1 | 0.03 | 0.73 | 0.00 | 0.42 | |||
| ΔG298 K, kJ mol–1 | 0.00 | 0.54 | 1.87 | 2.42 | |||
| ΔEc, kJ mol–1 | –25.77 | –25.02 | –27.15 | –27.28 | |||
| r(S–H ···S), Å | 2.879 | 2.846 | 2.843 | 2.830 | |||
| ∠(S–H···S), deg | 138.9 | 140.8 | 134.5 | 134.0 | |||
a
B2PLYP-D3(BJ)/def2-TVZP predictions, see the Supporting Information for B3LYP-D3(BJ) and ωB97XD/cc-pVTZ values.
b
Torsional substates denoted v = 0 and 1.
c
Rotational constants (A, B, C), Ray’s asymmetry parameter (κ = (2B – A – C)/(A – C)), Watson’s A-reduction centrifugal distortion constants (ΔJ, ΔJK, ΔK, δJ, δK) and torsional energy diference (ΔE10).
d
Standard errors in units of the last digit.
e
Number of transitions (N) and rms deviation (σ) of the fit.
f
Electric dipole moments (μα, α = a, b, c).
g
Relative energies corrected with the zero-point energy (ZPE), Gibbs energy (ΔG) at 100 and 298 K (1 atm) and complexation energy (ΔEc).