Thermal Rate Coefficients and Kinetic Isotope Effects for the Reaction OH + CH4 → H2O + CH3 on an ab Initio-Based Potential Energy Surface

被引：17

作者：

Li, Jun ^{[1
]}

Guo, Hua ^{[2
]}

机构：

[1] Chongqing Univ, Sch Chem & Chem Engn, Chongqing 401331, Peoples R China

[2] Univ New Mexico, Dept Chem & Chem Biol, Albuquerque, NM 87131 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2018年 / 122卷 / 10期

基金：

中国国家自然科学基金;

关键词：

TRANSITION-STATE THEORY; QUANTUM SCATTERING CALCULATIONS; POTENTIAL-ENERGY SURFACES; RATE CONSTANTS; AB-INITIO; RADICAL REACTIONS; REACTION DYNAMICS; FLASH-PHOTOLYSIS; SHOCK-TUBE; METHANE;

D O I：

10.1021/acs.jpca.8b01201

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Thermal rate coefficients for the title reaction and its various isotopologues are computed using a tunneling-corrected transition-state theory on a global potential energy surface recently developed by fitting a large number of high-level ab initio points. The calculated rate coefficients are found to agree well with the measured ones in a wide temperature range, validating the accuracy of the potential energy surface. Strong non-Arrhenius effects are found at low temperatures. In addition, the calculations reproduced the primary and secondary kinetic isotope effects. These results confirm the strong influence of tunneling to this heavy-light-heavy hydrogen abstraction reaction.

引用

页码：2645 / 2652

页数：8

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