Homogeneity and Markovity of electronic dephasing in liquid solutions

Abstract

The electronic dephasing dynamics of a solvated chromophore is formulated in terms of a non-Markovian master equation. Within this formulation, one describes the effect of the nuclear degrees of freedom on the electronic degrees of freedom in terms of a memory kernel function, which is explicitly dependent on the initial solvent configuration. In the case of homogeneous dynamics, this memory kernel becomes independent of the initial configuration. The Markovity of the dephasing process is also the most conveniently explored by comparing the results obtained via the non-Markovian master equation to these obtained via its Markovian counterpart. The homogeneous memory kernel is calculated for a two-state chromophore in liquid solution, and used to explore the sensitivity of photon echo signals to the heterogeneity and non-Markovity of the underlying solvation dynamics.