The simulation of electronic absorption spectrum of a chromophore coupled to a condensed phase environment: Maximum entropy versus singular value decomposition approaches

Abstract

We consider the problem of calculating the electronic absorption spectrum of a chromophore with intramolecular degrees of freedom coupled to a condensed phase environment. We approach this calculation in the framework of the imaginary-time path integral Monte Carlo techniques, and focus on the problem of the analytic continuation of the imaginary-time data to the real-time axis. Two alternative analytic continuation methods are considered: the maximum entropy method and the singular value decomposition method. An exactly solvable model is introduced to test the accuracy of these methods. Exact numerical results for the absorption spectra are compared to the spectra reconstructed by the analytic continuation methods; it is found that the singular value decomposition method gives systematically higher resolution than the maximum entropy method and is capable of reproducing the fine vibronic structure of the absorption spectrum.