物理化学学报 >> 2012, Vol. 28 >> Issue (08): 1892-1898.doi: 10.3866/PKU.WHXB201205241

理论与计算化学 上一篇    下一篇

YS+(1Σ+, 3Φ)与COS气相反应: YS++COS→YS2++CO的理论研究

杨树1,2, 杨晓梅3, 谢小光1   

  1. 1. 云南大学化学科学与工程学院, 昆明 650091;
    2. 昆明理工大学理学院, 昆明 650093;
    3. 云南中医学院, 昆明 650091
  • 收稿日期:2012-02-07 修回日期:2012-05-24 发布日期:2012-07-10
  • 通讯作者: 谢小光 E-mail:xgxie@ynu.edu.cn
  • 基金资助:

    国家自然科学基金(30930074)资助项目

Theoretical Study of Gas-Phase Reaction of YS+ (1Σ+, 3Φ) with COS: YS++COS→YS2++CO

YANG Shu1,2, YANG Xiao-Mei3, XIE Xiao-Guang1   

  1. 1. School of Chemical Science and Technology, Yunnan University, Kunming 650091, P. R. China;
    2. Faculty of Science, Kunming University of Science and Technology, Kunming 650093, P. R. China;
    3. Yunnan University of Traditional Chinese Medicine, Kunming 650091, P. R. China
  • Received:2012-02-07 Revised:2012-05-24 Published:2012-07-10
  • Contact: XIE Xiao-Guang E-mail:xgxie@ynu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (30930074).

摘要:

采用密度泛函B3LYP方法研究了硫化钇离子YS+ (1Σ+, 3Φ)与硫转移试剂COS在气相中的反应: YS++COS→YS2++CO. 在单重基态和三重激发态势能面上都找到了四条反应通道. 但是除一条反应通道之外, 其他的反应机理和几何结构变化趋势在不同的势能面上有很大不同. 实验中生成YS2+ 所表现出的吸热特征来自于在基态反应中的三条通道(A, B和C), 其活化势垒分别为28.3, 140.5和120.2 kJ·mol-1. 计算结果表明硫转移反应没有双态反应活性, 因此产物YS2+ 在低能量区的放热特征是由于基态反应物中还混有残留的激发态YS+.

关键词: 硫化钇离子, COS, 反应机理, B3LYP

Abstract:

The gas-phase reactions of YS+ (1Σ+, 3Φ) with an S-transfer reagent (COS), YS++COS→YS2++CO, were studied using density functional theory at the B3LYP/6-311+G* level. Four parallel reaction pathways were identified on both the ground- and excited-state surfaces. The mechanisms and the geometrical change trends on the different surfaces are quite different, except in the case of one reaction channel. The experimentally observed endothermic feature of the formation of YS2+ can be attributed to three reaction paths, A, B, and C, with calculation barriers of 28.3, 140.5, and 120.2 kJ mol-1, respectively, on the ground singlet surface. Our calculation results show that the title reactions have no two-state reactivity and the exothermic feature of the YS2+ cross-section observed in the experiments is attributed to reaction of the residual excited-state of YS+ in the reactants.

Key words: Yttrium sulfide cation, COS, Reaction mechanism, B3LYP

MSC2000: 

  • O643