To augment previous theoretical studies of thermochemical properties such as the electron affinity (EA) and bond dissociation enthalpy (${\mathrm{D}}_{298}^{\mathrm{o}}$) of neutral and anionic SF_n (with n = 1–6), further extensive theoretical computations using Gaussian-4 and Weizmann-1 and Weizmann-2 (G4/W1/W2) methods were carried out with extensive consideration of the role of the metastable conformational isomer of the ${\mathrm{S}\mathrm{F}}_4^{-}$ anion. The energy of the metastable conformer is 39 kJ/mol higher than that of the global minimum structure, and the barrier height between the metastable conformer and its global minimum was calculated to be 27 kJ/mol by the CCSD(T)/Aug-cc-pvQZ+d//MP2/cc-pvQZ+d method. Many of the discrepancies that have persisted between previous theoretical and experimental data can be explained more adequately by considering the metastable conformer. The difference in the EA calculated using the Gaussian-3 (G3) vs the W2 method for SF_n with n = 2–6 ranges from 0.12 eV to 0.21 eV, which is much larger than ±0.041 eV of the expected error for the G3 method. The difference in ${\mathrm{D}}_{298}^{\mathrm{o}}$ calculated using G3 vs W2 was also significant in several cases, especially for hypervalent fluorides with n = 3–6. The final results obtained with the W2 procedure are sufficiently converged to a chemical accuracy of ±4 kJ/mol ≈ ±0.04 eV for not only the EA but also ${\mathrm{D}}_{298}^{\mathrm{o}}$, for all neutral and anionic SF_n species with n = 1–6.

中文翻译：

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中性和阴离子氟化硫SFn（n = 1–6）的热化学：用理论的G4 / W1 / W2复合方法和SF4-阴离子的亚稳构构体的作用进行了探讨。

为了扩大对热化学性质（如电子亲和力（EA）和键解离焓（${\mathrm{d}}_{298}^{\mathrm{Ø}}$）中性和阴离子SF _n（n = 1-6），使用高斯4和Weizmann-1和Weizmann-2（G4 / W1 / W2）方法进行了更广泛的理论计算，同时广泛考虑了的亚稳态构象异构体${\mathrm{小号}\mathrm{F}}_4^{-}$阴离子。亚稳态构象异构体的能量比全局最小结构的能量高39 kJ / mol，并且通过CCSD（T）/ Aug-cc计算出亚稳态构象异构体与其全局最小值之间的势垒高度为27 kJ / mol。 -pvQZ + d // MP2 / cc-pvQZ + d方法。通过考虑亚稳态构象异构体，可以更充分地解释以前的理论和实验数据之间存在的许多差异。对于n = 2–6的SF _n，使用高斯3（G3）与W2方法计算的EA差异在0.12 eV至0.21 eV的范围内，远大于G3的预期误差的±0.041 eV方法。的区别${\mathrm{d}}_{298}^{\mathrm{Ø}}$在某些情况下，使用G3 vs W2计算得出的结果也很重要，尤其是对于n = 3–6的高价氟化物。通过W2程序获得的最终结果不仅对于EA，而且对于EA也足够收敛于±4 kJ / mol≈±0.04 eV的化学精度。${\mathrm{d}}_{298}^{\mathrm{Ø}}$，对于所有中性和阴离子SF _n物种，n = 1-6。