Theoretical study on the reaction of the ground state 2Δ of TiS+ with oxygen-transfer reagent:: TiS++H2O→TiO++H2S in the gas phase

被引:6
作者
Xie, XG [1 ]
Ye, S
Zhou, YM
Cao, H
Shi, NH
机构
[1] Yunnan Univ, Dept Chem, Kunming 650091, Peoples R China
[2] Yunnan Univ, Modern Biol Ctr, Kunming 650091, Peoples R China
来源
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2003年 / 624卷
关键词
ab initio; cationic titanium sulfide; oxygen-transfer reagent; reaction mechanism;
D O I
10.1016/S0166-1280(02)00496-7
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The reaction mechanism of the ground state (2)Delta of TiS+ with oxygen-transfer reagent: TiS+ + H2O --> TiO+ + H2S, in the gas phase has been proposed and investigated by ab initio methods with 6-31G** basis set for non-metal atoms and the effective core potentials of Lanl2dz for Ti. The reaction is proceeding via,two steps with seven stationary points (reactants, three intermediate complexes: (a), (b) and (c) two transition states: TS1 and TS2, and products) on the reaction potential surface which involved two 1,3-hydrogen shift reactions from oxygen atom to sulfur atom via a four-center transition state. The activation barriers of the two transition states are -54.0 and -65.1 kcal/mol, respectively, at MP4 (SDTQ)/6-31G**//MP2/6-31G** level plus zero-point energy relative to the reactants, which-indicates that cationic titanium sulfide is favorable to this type of reaction and the collision rate of-the reactants forming the complex (a) should be the main factor that determines the reaction rate. (C) 2003 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:17 / 22
页数:6
相关论文
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