Acta Phys. -Chim. Sin. ›› 2012, Vol. 28 ›› Issue (08): 1892-1898.doi: 10.3866/PKU.WHXB201205241

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

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).

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