论文标题
计算规范和微型典型集合中的反应速率常数
Calculation of Reaction Rate Constants in the Canonical and Microcanonical Ensemble
论文作者
论文摘要
规范插入理论是一种普遍的方法，可以描述隧道效应占主导地位时低温环境中化学反应的动力学。这是一种半经典理论，需要在颠倒的势能表面，所谓的激体顿及其二阶量子校正的计算上定位经典的周期轨道。这些校正的计算通常涉及矩阵对角线化。在本文中，我们提出了一种替代方法，该方法需要仅求解涉及稀疏矩阵的方程式线性系统。此外，提出的方法提供了一种可靠且数值稳定的方法来获得多维系统中的稳定性参数，这在微跨式插入理论的背景下特别感兴趣。
Canonical instanton theory is a widespread approach to describe the dynamics of chemical reactions in low temperature environments when tunneling effects become dominant. It is a semiclassical theory which requires locating classical periodic orbits on the upside-down potential energy surface, so-called instantons, and the computation of second order quantum corrections. The calculation of these corrections usually involves a matrix diagonalization. In this paper we present an alternative approach, which requires to solve only linear systems of equations involving sparse matrices. Furthermore, the proposed method provides a reliable and numerically stable way to obtain stability parameters in multidimensional systems, which are of particular interest in the context of microcanonical instanton theory.
