Mixed quantum classical calculation of proton transfer reaction rates: From deep tunneling to over the barrier regimes

doi:10.1063/1.4873135

CORC > 化学研究所 > 中国科学院化学研究所

	Mixed quantum classical calculation of proton transfer reaction rates: From deep tunneling to over the barrier regimes
	Xie, Weiwei; Xu, Yang; Zhu, Lili; Shi, Qiang
刊名	JOURNAL OF CHEMICAL PHYSICS
	2014-05-07
卷号	140 期号:17
ISSN号	0021-9606
DOI	10.1063/1.4873135
英文摘要	We present mixed quantum classical calculations of the proton transfer (PT) reaction rates represented by a double well system coupled to a dissipative bath. The rate constants are calculated within the so called nontraditional view of the PT reaction, where the proton motion is quantized and the solvent polarization is used as the reaction coordinate. Quantization of the proton degree of freedom results in a problem of non-adiabatic dynamics. By employing the reactive flux formulation of the rate constant, the initial sampling starts from the transition state defined using the collective reaction coordinate. Dynamics of the collective reaction coordinate is treated classically as over damped diffusive motion, for which the equation of motion can be derived using the path integral, or the mixed quantum classical Liouville equation methods. The calculated mixed quantum classical rate constants agree well with the results from the numerically exact hierarchical equation of motion approach for a broad range of model parameters. Moreover, we are able to obtain contributions from each vibrational state to the total reaction rate, which helps to understand the reaction mechanism from the deep tunneling to over the barrier regimes. The numerical results are also compared with those from existing approximate theories based on calculations of the non-adiabatic transmission coefficients. It is found that the two-surface Landau-Zener formula works well in calculating the transmission coefficients in the deep tunneling regime, where the crossing point between the two lowest vibrational states dominates the total reaction rate. When multiple vibrational levels are involved, including additional crossing points on the free energy surfaces is important to obtain the correct reaction rate using the Landau-Zener formula. (C) 2014 AIP Publishing LLC.
语种	英语
出版者	AMER INST PHYSICS
WOS记录号	WOS:000336048000007
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/51543]
专题	中国科学院化学研究所
通讯作者	Xie, Weiwei
作者单位	Chinese Acad Sci, Inst Chem, State Key Lab Struct Chem Unstable & Stable Speci, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
推荐引用方式 GB/T 7714	Xie, Weiwei,Xu, Yang,Zhu, Lili,et al. Mixed quantum classical calculation of proton transfer reaction rates: From deep tunneling to over the barrier regimes[J]. JOURNAL OF CHEMICAL PHYSICS,2014,140(17).
APA	Xie, Weiwei,Xu, Yang,Zhu, Lili,&Shi, Qiang.(2014).Mixed quantum classical calculation of proton transfer reaction rates: From deep tunneling to over the barrier regimes.JOURNAL OF CHEMICAL PHYSICS,140(17).
MLA	Xie, Weiwei,et al."Mixed quantum classical calculation of proton transfer reaction rates: From deep tunneling to over the barrier regimes".JOURNAL OF CHEMICAL PHYSICS 140.17(2014).