Quantum instanton calculation of rate constant for CH4 OH &rarr CH3 H2O reaction: Torsional anharmonicity and kinetic isotope effect

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	Quantum instanton calculation of rate constant for CH4 OH &rarr CH3 H2O reaction: Torsional anharmonicity and kinetic isotope effect
	Wang, Wenji ; Zhao, Yi ; Zhao Y(赵仪)
刊名	http://dx.doi.org/10.1063/1.4768874
	2012
关键词	Carrier mobility Energy barriers Free energy Isotopes Quantum electronics
英文摘要	Thermal rate constants for the title reaction are calculated by using the quantum instanton approximation within the full dimensional Cartesian coordinates. The results reveal that the quantum effect is remarkable for the reaction at both low and high temperatures, and the obtained rates are in good agreement with experimental measurements at high temperatures. Compared to the harmonic approximation, the torsional anharmonic effect of the internal rotation has a little influence on the rates at low temperatures, however, it enhances the rate by about 20% at 1000 K. In addition, the free energy barriers for the isotopic reactions and the temperature dependence of kinetic isotope effects are also investigated. Generally speaking, for the title reaction, the replacement of OH with OD will reduce the free energy barrier, while substituting D for H (connected to C) will increase the free energy barrier. 漏 2012 American Institute of Physics.
语种	英语
出版者	American Institute of Physics
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/89618]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Wang, Wenji,Zhao, Yi,Zhao Y. Quantum instanton calculation of rate constant for CH4 OH &rarr CH3 H2O reaction: Torsional anharmonicity and kinetic isotope effect[J]. http://dx.doi.org/10.1063/1.4768874,2012.
APA	Wang, Wenji,Zhao, Yi,&赵仪.(2012).Quantum instanton calculation of rate constant for CH4 OH &rarr CH3 H2O reaction: Torsional anharmonicity and kinetic isotope effect.http://dx.doi.org/10.1063/1.4768874.
MLA	Wang, Wenji,et al."Quantum instanton calculation of rate constant for CH4 OH &rarr CH3 H2O reaction: Torsional anharmonicity and kinetic isotope effect".http://dx.doi.org/10.1063/1.4768874 (2012).