SiH4 + H→SiH3 + H2反应的全球12维从头算势能面及动力学研究

A global 12-dimensional ab initio potential energy surface and dynamical studies for the SiH4+H-->SiH3+H2 reaction.

作者信息

Wang Manhui, Sun Xiaomin, Bian Wensheng, Cai Zhengting

机构信息

Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China.

出版信息

J Chem Phys. 2006 Jun 21;124(23):234311. doi: 10.1063/1.2203610.

DOI:10.1063/1.2203610

PMID:16821922

Abstract

A global 12-dimensional ab initio interpolated potential energy surface (PES) for the SiH(4)+H-->SiH(3)+H(2) reaction is presented. The ab initio calculations are based on the unrestricted quadratic configuration interaction treatment with all single and double excitations together with the cc-pVTZ basis set, and the modified Shepard interpolation method of Collins and co-workers [K. C. Thompson et al., J. Chem. Phys. 108, 8302 (1998); M. A. Collins, Theor. Chem. Acc. 108, 313 (2002); R. P. A. Bettens and M. A. Collins, J. Chem. Phys. 111, 816 (1999)] is applied. Using this PES, classical trajectory and variational transition state theory calculations have been carried out, and the computed rate constants are in good agreement with the available experimental data.

摘要

本文给出了SiH(4)+H-->SiH(3)+H(2)反应的一个全局12维从头算插值势能面（PES）。从头算计算基于采用cc-pVTZ基组的含所有单双激发的无限制二次组态相互作用处理方法，并应用了Collins及其同事的改进型谢泼德插值方法[K.C.汤普森等人，《化学物理杂志》108, 8302 (1998)；M.A.柯林斯，《理论化学学报》108, 313 (2002)；R.P.A.贝滕斯和M.A.柯林斯，《化学物理杂志》111, 816 (1999)]。利用该势能面进行了经典轨迹和变分过渡态理论计算，计算得到的速率常数与现有的实验数据吻合良好。