Implementation of a microcanonical variational transition state theory for direct dynamics calculations of rate constants

被引：0
作者：
Yan Wang
Ying Qian
Wenlin Feng
Ruozhuang Liu
机构：
[1] Beijing Normal University,Department of Chemistry
[2] Beijing Polytechnic University,College of Environment and Energy Engineering
来源：
Science in China Series B: Chemistry | 2003年 / 46卷
关键词：
RRKM theory; rate constant; microcanonical variational transition state theory; direct ; dynamics; tunneling effect;
D O I：
暂无
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学科分类号：
摘要：
An implementation of the variational quantum RRKM program is presented to utilize the direct ab initio dynamics approach for calculating k(tE, J), k(E) and k(T) within the framework of the microcanonical transition state (μTST) and microcanonical variational TST (μVT) theories. An algorithm including tunneling contributions in Beyer-Swinehart method for calculating microcanonical rate constants is also proposed. An efficient piece-wise interpolation method is developed to evaluate the Boltzmann integral in calculation of thermal rate constants. Calculations on several test reactions, namely the H(D)2CO→ H(D)2 + CO, CH2CO→CH2 + CO and CH4 + H→CH3 + H2 reactions, show that the results are in good agreement with the previous rate constants calculations. This approach would require much less computational resource.
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页码：225 / 233
页数：8
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