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arXiv · 1211.1469

Reduced hierarchy equations of motion approach with Drude plus Brownian spectral distribution: Probing electron transfer processes by means of two- dimensionalcorrelation spectroscopy

Yoshitaka Tanimura
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Abstract

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.

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Yoshitaka Tanimura. 2012-11-07. Reduced hierarchy equations of motion approach with Drude plus Brownian spectral distribution: Probing electron transfer processes by means of two- dimensionalcorrelation spectroscopy. https://doi.org/10.1063/1.4766931

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