Theoretical Study on the Dehydrogenation Reaction of H_2S by VS^+ (~3Σ^-)

作     者：GAO Shu-Lin LIU Zheng-Mei XIE Xiao-Guang 

作者机构：Department of Chemistry Yunnan University Kunming 650091 China School of Physics and Chemistry Guizhou Normal University Guiyang 550001 China 

出 版 物：《Chinese Journal of Structural Chemistry》 (结构化学（英文）)

年 卷 期：2005年第24卷第10期

页      面：1111-1116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] 070303[理学-有机化学] 0703[理学-化学] 070301[理学-无机化学] 

主　　题：density functional theory cationic transition metal sulfide,dehydrogenation reaction reaction mechanism 

摘      要：The dehydrogenation reaction of H2S by the ^3Σ^- ground state of VS^＋： VS^＋ ＋ H2S → VS2^＋ ＋ H2 has been studied by using Density Functional Theory （DPT） at the B3LYP/DZVP level. It is found that the reaction proceeds along two possible pathways （A and B） yielding two isomer dehydrogenation products VS2^＋-1 （^3B2） and VS2^＋-2 （^3A1）, respectively. For both pathways, the reaction has a two-step-reaction mechanism that involves the migration of two hydrogen atoms from S2 to V^＋, respectively. The migration of the second hydrogen via TS3 and that of the first via TS4 are the rate-determining steps for pathways A and B, respectively. The activation energy is 17.4 kcal/mol for pathway A and 22.8 kcal/mol for pathway B relative to the reactants. The calculated reaction heat of 9.9 kcal/mol indicates the endothermicity of pathway A and that of -11.9 kcal/mol suggests the exothermicity of pathway B.