在最近的势能面上，对 H + CH(4) → H(2) + CH(3)的全维量子反应速率进行计算。

Full-dimensional quantum reaction rate calculations for H + CH(4) → H(2) + CH(3) on a recent potential energy surface.

机构信息

Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, 33615 Bielefeld, Germany.

出版信息

J Phys Chem A. 2010 Sep 16;114(36):9617-22. doi: 10.1021/jp911880u.

PMID:20518477

Abstract

The thermal rate constant of the H + CH(4) → H(2) + CH(3) reaction on the recent potential energy surface (PES) of Corchado et al (CBE) (Corchado, J. C.; Bravo, J. L.; Espinosa-Garcia, J. J. Chem. Phys. 2009, 130, 184314) is computed employing the state-averaged multiconfigurational time-dependent Hartree approach in the temperature range 250-500 K. The CBE PES is global and is based on an analytic functional form that is fast to evaluate. This surface is therefore potentially useful for testing new quantum dynamics methods, and reference rate constants for this purpose are presented here. The thermal rate constants obtained are compared to results previously obtained on an accurate PES particularly designed for thermal rate constant calculations (Wu, T.; Werner, H.; Manthe, U. Science 2004, 306, 2227). The two sets of rate constants are found to agree almost perfectly.

摘要

采用态平均多组态含时微扰理论在 250-500 K 的温度范围内计算了 Corchado 等人（CBE）（Corchado, J. C.; Bravo, J. L.; Espinosa-Garcia, J. J. Chem. Phys. 2009, 130, 184314）最近势能面上的 H + CH(4) → H(2) + CH(3) 反应的热速率常数。CBE 势能面是全局的，并且基于快速评估的解析函数形式。因此，该表面对于测试新的量子动力学方法可能很有用，并且此处提供了用于此目的的参考速率常数。获得的热速率常数与专门为热速率常数计算设计的准确势能面（Wu, T.; Werner, H.; Manthe, U. Science 2004, 306, 2227）上先前获得的结果进行了比较。发现这两组速率常数几乎完全一致。