On the alternatives for bath correlators and spectral densities from mixed quantum-classical simulations

TL;DR

This paper examines methods for deriving spectral densities from mixed quantum-classical simulations, analyzing their accuracy and applying corrections, with a case study on the Fenna-Matthews-Olson complex.

Contribution

It introduces a simple model to understand when ground state QM/MM yields correct energy gaps and evaluates semiclassical corrections for spectral densities in open quantum systems.

Findings

Harmonic prefactor is more suitable for the Fenna-Matthews-Olson complex.

Higher order correlators provide additional bath information.

Semiclassical corrections improve spectral density accuracy.

Abstract

We investigate on the procedure of extracting a "spectral density" from mixed QM/MM calculations and employing it in open quantum systems models. In particular, we study the connection between the energy gap correlation function extracted from ground state QM/MM and the bath spectral density used as input in open quantum system approaches. We introduce a simple model which can give intuition on when the ground state QM/MM propagation will give the correct energy gap. We also discuss the role of higher order correlators of the energy-gap fluctuations which can provide useful information on the bath. Further, various semiclassical corrections to the spectral density, are applied and investigated. Finally, we apply our considerations to the photosynthetic Fenna-Matthews-Olson complex. For this system, our results suggest the use of the Harmonic prefactor for the spectral density rather than the Standard one, which was employed in the simulations of the system carried out to date.