Zhao Yi, Han MiaoMiao, Liang WanZhen, Nakamura Hiroki
Department of Chemical Physics, University of Science and Technology of China, Hefei, 230026, P. R. China.
J Phys Chem A. 2007 Mar 22;111(11):2047-53. doi: 10.1021/jp066565k. Epub 2007 Feb 21.
The previously formulated semiclassical theory (Zhao, Liang, and Nakamura, J. Phys. Chem. A 2006, 110, 8204) is used to study electron transfer in the Marcus inverted case by considering multidimensional potential energy surfaces of donor and acceptor. The Zhu-Nakamura formulas of nonadiabatic transition in the case of Landau-Zener type are incorporated into the approach. The theory properly takes into account the nonadiabatic transition coupled with the nuclear tunneling and can cover the whole range from weak to strong coupling regime uniformly under the assumption of fast solvent relaxation. The numerical calculations are performed for the 12-dimensional model of shifted harmonic oscillators and demonstrate that the reaction rate with respect to the electronic coupling shows a maximum, confirming the adiabatic suppression in the strong coupling limit. The adiabatic suppression is dramatically reduced by the effect of nuclear tunneling compared to the case that the Landau-Zener formula is used. The possible extension and applications to the case of the slow solvent dynamics are discussed.
先前提出的半经典理论（Zhao、Liang和Nakamura，《物理化学杂志A》2006年，第110卷，第8204页）用于通过考虑供体和受体的多维势能面来研究马库斯反转情况下的电子转移。将朗道 - 齐纳类型情况下非绝热跃迁的朱 - 中村公式纳入该方法。该理论在快速溶剂弛豫的假设下，恰当地考虑了与核隧穿耦合的非绝热跃迁，并且能够统一覆盖从弱耦合到强耦合的整个范围。对平移谐振子的12维模型进行了数值计算，结果表明反应速率相对于电子耦合呈现出最大值，证实了在强耦合极限下的绝热抑制。与使用朗道 - 齐纳公式的情况相比，核隧穿效应显著降低了绝热抑制。还讨论了对慢溶剂动力学情况的可能扩展和应用。
