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Electron Transfer Theory Revisit: Motional Narrowing Induced Non-Markovian Rate Processes
Ying Chen,Rui-xue Xu,Hong-wei Ke,Yi-jing Yan*
1.Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Hefei 230026, China;2.Department of Chemistry, Hong Kong University of Science and Technology, Hong Kong
Abstract:
While the exact theory of chemical reaction rate processes is always non-Markovian, experimental rates do often show practically Markovian that supports kinetics rate constant description. In this work, we propose to use the Kubo's motional narrowing line shape function to characterize the Markovian character of the simplest two-state electron transfer reaction system. On the basis of analytical results, we demonstrate the related Markovianicity parameter as an interplay between the °uctuating solvent environment and the coherent transfer coupling. It is found that a non-Markovian rate process is most likely to occur in a symmetric system in the fast solvent modulation regime, where the resonant tunneling enhancement plays the important role. The e?ect of quantum solvation on electron transfer, which is dominant in the fast modulation regime, will also be highlighted.
Key words:  Non-markovian rate, Quantum solvation, Electron transfer
FundProject:RGC Hong Kong (604006), NNSF of China (50121202), National Basic Research Program of China (2006CB922004), NNSF of China (20403016 and 20533060) and Ministry of Education of China (NCET-05-0546)
电子转移速率理论研究:运动谱窄化所导致的非马尔可夫电子转移过程
陈英1, 徐瑞雪1, 柯宏伟2, 严以京*1,3
1.中国科学技术大学合肥微尺度物质科学国家实验室,合肥230026;2.香港科技大学化学系,香港;3.b. 香港科技大学化学系,香港
摘要:
严格的速率方程理论得到的总是非马尔可夫的,可是大部分实验都可以用马尔可夫的、即传统的速率常数基础上的反应动力学方程来描述.针对这一问题研究了电子转移过程中的马尔可夫/非马尔可夫特性.以最简单的两态电子转移反应为体系,以其在德拜溶剂中的严格动力学解为标定,采用光谱领域著名的Kubo运动谱窄化线型函数及其特性参数来描述电子转移过程中的马尔可夫/非马尔可夫本质.该马尔可夫特性参数是相干转移耦合与溶剂环境涨落相互影响共同作用的结果,以它为基础说明了大部分实验确实可以通过传统的速率方程来描述,而非马尔可夫速率过程最
关键词:  非马尔可夫过程,量子溶剂化,电子转移
DOI:10.1088/1674-0068/20/04/438-444
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