Theoretical study on the reaction of VS^+(~3∑^-,~1Γ)with CO

作     者：Shi Wen Yu Li Qing Yin Li Feng Yao Ming Li Xiao Guang Xie 

作者机构：Department of Chemistry Yunnan University Kunming 650091 China 

出 版 物：《Chinese Chemical Letters》 (中国化学快报（英文版）)

年 卷 期：2008年第19卷第8期

页      面：1008-1011页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 070301[理学-无机化学] 

基　　金：the National Natural Science Foundation of China(No.20563005) the High Performance Computer Center of Yunnan University 

主　　题：Vanadium sulfide ion CO Reaction CCSD(T) 

摘      要：Two possible reaction mechanisms of VS^＋（^3∑^-, 1^Г） with CO in the gas phase have been studied by using B3LYP/TZVP and CCSD（T）/6-311＋G （3df, 3pd） methods： the O/S exchange reaction （VS^＋＋CO→VO^＋＋CS） and the S-transfer reaction （VS^＋ ＋ CO → V^＋ ＋ COS）. The two reactions proceed via two-step and one-step mechanism, respectively. The barriers of the triplet and singlet PESs are 30.6 and 50.9 kcal/mol, respectively, for O/S exchange reaction and 7.3 and 50.2 kcal/mol, respectively, for the S-transfer reaction. The results indicate that the triplet ground state reaction is more favorable, and the S-transfer reaction is more favorable than the O/S exchange reaction, which is in good agreement with the experimental observation.