H2CS3和H2CS4的电子结构：一项实验与理论研究。

Electronic structure of H2CS3 and H2CS4: an experimental and theoretical study.

作者信息

Li Yimin, Zeng Xiaoqing, Sun Qiao, Li Haiyang, Ge Maofa, Wang Dianxun

机构信息

Department of Chemistry, Shaoxing University, Shaoxing, Zhejiang 312000, PR China.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2007 Apr;66(4-5):1261-6. doi: 10.1016/j.saa.2006.06.016. Epub 2006 Jun 27.

DOI:10.1016/j.saa.2006.06.016

PMID:16919498

Abstract

The HeI photoelectron spectra of H2CS3 and H2CS4 in the gas phase have been obtained for the first time. A complete theoretical study involving the calculation of the ionization energies using orbital valence Green's functional (OVGF) and population analysis was performed. Calculations of cation-radical forms were carried out in order to interpret the main characters of the six highest occupied molecular orbitals (HOMOs). The first vertical ionization potentials are 8.74 and 8.56eV for H2CS3 and H2CS4, and attributed to {9b2(nS(C=S))}-1 and {8a"(3ppi*(S-S), nS)}-1, respectively. Meanwhile, the energy sequence of three types of sulfur 3p lone-pair have been discussed: 3ppi(S-S)<nS(C=S)<n(S3p), and an energy splitting DeltaE=2.06 eV of 3ppi(S-S) and 3ppi(S-S) orbitals in H2CS4 is observed.

摘要

首次获得了气相中H2CS3和H2CS4的HeI光电子能谱。进行了一项完整的理论研究，包括使用轨道价格林函数（OVGF）计算电离能和布居分析。为了解释六个最高占据分子轨道（HOMO）的主要特征，对阳离子自由基形式进行了计算。H2CS3和H2CS4的第一垂直电离势分别为8.74和8.56eV，分别归因于{9b2(nS(C=S))}-1和{8a"(3ppi*(S-S), nS)}-1。同时，讨论了三种类型硫3p孤对电子的能量顺序：3ppi(S-S)*<nS(C=S)<n(S3p)，并观察到H2CS4中3ppi(S-S)和3ppi(S-S)*轨道的能量分裂ΔE = 2.06 eV。