S_3分子的几何结构:分子轨道从头算和Franck-Condon分析(英文)

The geometry structure of S_3 molecule:ab initio calculation and Franck-Condon analysis

在考虑Duschinsky效应情况下，给出了多维Franck-Condon因子的理论计算公式；利用分子轨道从头算，完成了S3分子的X^-1A1态和S3^-分子的X^-2B1态的几何结构优化和谐振频率分析，模拟了S3^-的光电子能谱．在光谱模拟中，利用迭代Franck—Condon分析，得到了S3分子的X^-1A1态的几何构型参数：r（SS）=1．94±0．02A和∠（（S-S-S）=117．35±0．05°．由所得的S3分子的键角对Nimols等人得的结果[J．Phys．Chem．1986，90：2574]给出一个新的解释．

A theoretical method to calculate multidimensional Franck-Condon factors including Duschinsky effects is described and used to simulate the vibrationally resolved photoelectron spectra of S3^- combining with ab initio molecular orbital calculations. Geometry optimizations and harmonic vibrational frequency calculations have been performed on the X^-1A1 state of S3 and X^-2B1 state of S3^-, In addition, the equilibrium geometry parameters, r （SS） = 1.94±0.02 A and ∠（S-S-S） = 117.35 ±0.05°,of the X^-1A1 state of S3,are derived by employing an iterative Franck-Condon analysis in the spectral simulation. Our conclusions concerning the angel of S3 suggest a new interpretation of the results of Nimols et al [J. Phys. Chem. 1986,90： 2574].