Anhui Province Key Laboratory of Optoelectric Materials Science and Technology, Anhui Normal University, Wuhu, Anhui 241000, China.
State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
J Chem Phys. 2019 Jan 28;150(4):044302. doi: 10.1063/1.5080458.
As is well-known, the S molecule is a ubiquitous intermediate in the combustion, atmosphere, and interstellar space. The six low-lying bound states of S have been characterized via photoelectron velocity map imaging and a high-level multi-reference configuration interaction method with the Davidson correction. Spectroscopic constants have been extracted by fitting the potential energy curves extrapolated to the complete basis set limit with a series of Dunning's correlation-consistent basis sets: aug-cc-pV(Q, 5)Z. The calculated spectroscopic parameters well reproduce the experimental results in this work. On the basis of the theoretical calculations, Franck-Condon simulations are performed to assign six adjacent electronic states, especially for three higher overlapping electronic states (cΣ , A'Δ, and AΣ ). The dissociation energy D of the S is evaluated to be 4.111 (4) eV in this work, in agreement with the theoretical prediction (4.056 eV).
众所周知，S 分子是燃烧、大气和星际空间中普遍存在的中间体。通过光电离速度成像和带有 Davidson 修正的高精度多参考组态相互作用方法，已经对 S 的六个低能束缚态进行了特征描述。通过使用一系列 Dunning 的相关一致基组（aug-cc-pV(Q, 5)Z）将外推至完全基组极限的势能曲线进行拟合，提取了光谱常数。计算的光谱参数很好地再现了本工作中的实验结果。在此基础上，进行了 Franck-Condon 模拟，以分配六个相邻的电子态，特别是三个重叠较高的电子态（cΣ 、A'Δ 和 AΣ ）。本工作中 S 的离解能 D 评估为 4.111（4）eV，与理论预测（4.056 eV）一致。
