多原子反应的最小作用量隧穿传输系数

Least-Action Tunneling Transmission Coefficient for Polyatomic Reactions.

作者信息

Meana-Pañeda Rubén, Truhlar Donald G, Fernández-Ramos Antonio

机构信息

Department of Physical Chemistry, Faculty of Chemistry, University of Santiago de Compostela, 15782 Santiago de Compostela, Spain, and Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street S. E., Minneapolis, Minnesota 55455-0431.

出版信息

J Chem Theory Comput. 2010 Jan 12;6(1):6-17. doi: 10.1021/ct900420e.

DOI:10.1021/ct900420e

PMID:26614314

Abstract

We present a new least-action variational approximation for tunneling in polyatomic reactions based on the procedure developed by Garrett and Truhlar for atom-diatom reactions. (63) The method calculates the semiclassical ground-state tunneling probability at every tunneling energy by minimizing the value of imaginary action integral along a family of paths ranging from the minimum energy path to the straight path. The method is illustrated by applications to two hydrogen-atom abstraction reactions from methane using analytical potential energy surfaces.

摘要

我们基于加勒特（Garrett）和特鲁哈拉（Truhlar）为原子-双原子反应所开发的程序，提出了一种用于多原子反应隧穿的新的最小作用量变分近似方法。（63）该方法通过沿着从最小能量路径到直线路径的一系列路径最小化虚作用量积分的值，来计算每个隧穿能量下的半经典基态隧穿概率。通过使用解析势能面将该方法应用于两个从甲烷中提取氢原子的反应来说明这一方法。