May Volkhard
Institut fur Physik, Humboldt-Universitat zu Berlin, Newtonstrasse 15, D-12489 Berlin, Germany.
J Chem Phys. 2008 Sep 21;129(11):114109. doi: 10.1063/1.2976150.
Long-range electronic excitation energy transfer is studied in the framework of a generalized master equation approach, which offers a systematic account for higher-order processes. Bridge molecule mediated transfer is confronted with the direct excitation energy exchange via photon emission and absorption. It is the central aim of this paper to present a systematic study of fourth-order rates, which describe both types of transfer processes characterized by the presence of intermediate states. While such a Liouville space formulation of rates is known from bridge mediated transfer, it is new for the case of photon mediated processes. In the former case, however, a novel approach to account for intermediate state relaxation is introduced. Finally and for illustration, some estimates are offered for the length dependence of the various discussed transfer rates.
在广义主方程方法的框架内研究了长程电子激发能量转移，该方法为高阶过程提供了系统的描述。桥分子介导的转移与通过光子发射和吸收的直接激发能量交换相对比。本文的核心目标是对四阶速率进行系统研究，四阶速率描述了以中间态存在为特征的两种转移过程。虽然这种速率的刘维尔空间表述在桥介导转移中是已知的，但对于光子介导过程的情况却是新的。然而，在前一种情况下，引入了一种考虑中间态弛豫的新方法。最后，为了说明，给出了各种讨论的转移速率对长度依赖性的一些估计。
