Department of Physics, University of Hamburg, Centre for Free Electron Laser Science, DESY, Notkestrasse 85, D-22607 Hamburg, Germany.
J Chem Phys. 2012 Dec 14;137(22):22A550. doi: 10.1063/1.4766931.
We theoretically investigate an electron transfer (ET) process in a dissipative environment by means of two-dimensional (2D) correlation spectroscopy. We extend the reduced hierarchy equations of motion approach to include both overdamped Drude and underdamped brownian modes. While the overdamped mode describes the inhomogeneity of a system in the slow modulation limit, the underdamped mode expresses the primary vibrational mode coupled with the electronic states. We outline a procedure for calculating 2D correlation spectrum that incorporates the ET processes. The present approach has the capability of dealing with system-bath coherence under an external perturbation, which is important to calculate nonlinear response functions for non-markovian noise. The calculated 2D spectrum exhibits the effects of the ET processes through the presence of ET transition peaks along the Ω(1) axis, as well as the decay of echo signals.
我们通过二维（2D）相关光谱理论研究耗散环境中的电子转移（ET）过程。我们将约化的层次运动方程方法扩展到包含过阻尼 Drude 模式和欠阻尼布朗模式。过阻尼模式在慢调制极限下描述系统的非均匀性，而欠阻尼模式则表示与电子态耦合的主要振动模式。我们概述了一种计算包含 ET 过程的 2D 相关光谱的方法。本方法具有在外部扰动下处理系统-浴相干性的能力，这对于计算非马尔可夫噪声的非线性响应函数很重要。计算出的 2D 谱通过在 Ω(1) 轴上出现 ET 跃迁峰以及回波信号的衰减，显示出 ET 过程的影响。
