Table 1
Predicted and experimentally determined spectroscopic parameters of the Z and E isomer in the ground state (A reduction, Ir representation).
| Z isomer | E isomer | ||||
|---|---|---|---|---|---|
| Parameters | Calculated(a) | Groner et al. (1987) | This work | Calculated(a) | This work |
| A/MHz | 9774.223 | 9812.1614(54) | 9812.1796(15)(b) | 9741.906 | 9781.9611(59) |
| B/MHz | 4176.409 | 4168.2347(29) | 4168.22656(17) | 4196.015 | 4189.31394(48) |
| C/MHz | 2975.830 | 2975.1826(29) | 2975.16898(21) | 2982.875 | 2983.20974(68) |
| ΔJ/kHz | 0.751 | 0.859(32) | 0.77395(15) | 0.743 | 0.765934(93) |
| ΔJK/kHz | 14.628 | 15.75(12) | 15.66422(61) | 14.012 | 15.0050(19) |
| Δκ/kHz | −4.952 | −7.00(52) | −5.837(12) | −4.767 | −5.675(22) |
| δJ/kHz | 0.249 | 0.2687(39) | 0.258324(29) | 0.244 | 0.253809(61) |
| δK/kHz | 8.799 | 9.028(72) | 9.4666(15) | 8.348 | 8.9534(44) |
| ΦJ/mHz | 0.356 | – | 0.526(40) | 0.324 | [0.324](c) |
| ΦJK/Hz | 0.131 | – | 0.1491(14) | 0.114 | 0.12429(63) |
| ΦKJ/Hz | −0.278 | – | −0.3298(49) | −0.222 | −0.2517(26) |
| ΦK/Hz | 0.191 | – | [0.191](c) | 0.132 | [0.132](c) |
| ϕJ/mHz | 0.180 | – | [0.180](c) | 0.158 | [0.158](c) |
| ϕJK/Hz | 0.067 | – | 0.07646(65) | 0.059 | 0.0638(11) |
| ϕK/Hz | 0.296 | – | 0.361(10) | 0.269 | [0.269](c) |
| ∈10/MHz | – | – | −17.416(31) | – | −35.698(63) |
| [(B − C)/4]10/kHz | – | – | – | – | 0.223(35) |
| [(B + C)/2]10/kHz | – | – | – | – | 0.810(59) |
| ρ/Unitless | 0.039 | – | 0.040368(94) | 0.037 | 0.03753(10) |
| β/° | 35.090 | – | 33.657(62) | 39.550 | 37.08(10) |
| V3 (d)/cm−1 | 532.407 | 593.5(89) | 572.59(14) | 464.367 | 508.05(22) |
| Ια (e)/uÅ2 | 3.17 | 3.038(56) | 3.2177(53) | 3.16 | 3.1379(86) |
| ΔΕΕ−Α (e)/MHz | – | – | 52.251(94) | – | 107.09(19) |
| ∠(i, a) (e)/° | 58.692 | 57.68(61) | 57.463(61) | 62.455 | 60.462(93) |
| ∠(i, b) (e)/° | 31.308 | – | 32.537(61) | 27.545 | 29.538(93) |
| ∠(i, c) (e)/° | 90.00 | – | [90.00](f) | 90.00 | [90.00](f) |
| Jmin/Jmax | – | 2/38 | 2/53 | – | 24/53 |
 |
– | 0/11 | 0/36 | – | 0/25 |
| AN/EN (g) | – | 50/50 | 468/531 | – | 206/213 |
| σfit (h)/MHz | – | – | 0.036 | – | 0.043 |
| σw (h)/Unitless | – | – | 1.081 | – | 1.263 |
Notes – (a)Parameters estimated at the DFT/B3LYP/6-311++G(2d,3p) level of theory. (b)The numbers in parentheses are 1σ uncertainties in units of the last decimal digits. The ERHAM program (Groner 1997) was used for the analysis.(c)Fixed to the calculated value, which is usually a preferred constraint against the zero or poorly determined value (Urban & Sarka 1990). (d)Obtained from the XIAM (Hartwig & Dreizler 1996) analysis of solely non-overlapped rotational transitions. (e)Derived parameter. Ια is the moment of inertia of the methyl top, ΔΕΕ−Α is the torsional energy difference, and ∠(i, a/b/c) are the angles between the internal rotation axis i and the principal axes a, b, c. (f)Fixed value due to Cs symmetry. (g)Number of the A- and E-symmetry components in the fit. (h)Root mean square deviation of the fit. (i)Weighted deviation of the fit.
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