Thermal rate constant calculation using flux–flux autocorrelation functions: Application to Cl+H2→HCl+H reaction
Thermal rate constant calculation using flux–flux autocorrelation functions: Application to Cl+H2→HCl+H reaction
复制标题
使用通量-通量自相关函数计算热速率常数：应用于 Cl+H2→HCl+H 反应
DOI：
10.1063/1.474959
复制
发表时间：
1997
影响因子：
4.4
通讯作者：
W. Miller
中科院分区：
文献类型：
--
作者：
Haobin Wang;W. Thompson;W. Miller
最近，Thompson和米勒[J.Chem.Phys.106，142（1997）]介绍了一种有效的方法，用于使用具有吸收边界条件的通量-通量自相关函数计算热速率常数。该方法使用迭代方法来利用玻尔兹曼化通量算子的低秩特征，随后仅传播对速率常数有显著贡献的本征向量。本文用该方法计算了200-1500 °K范围内Cl+ H_2 →HCl+H反应的热速率常数。总角动量的处理，采用身体固定轴框架，无论是准确的，也通过各种近似。与以前的精确和近似的理论结果进行了比较。
An efficient method was recently introduced by Thompson and Miller [J. Chem. Phys. 106, 142 (1997)] for calculating thermal rate constants using the flux–flux autocorrelation function with absorbing boundary conditions. The method uses an iterative method to exploit the low rank feature of the Boltzmannized flux operator and subsequently only propagates the eigenvectors that have significant contributions to the rate constant. In the present article, this method is used to calculate the thermal rate constants of the Cl+H2→HCl+H reaction in the temperature range of 200–1500 °K. Total angular momentum is treated by employing the body-fixed axis frame, both exactly and also via various approximations. Comparisons with previous exact and approximate theoretical results are made.