# Calculation of coherences in Foerster and modified Redfield theories of excitation energy transfer

## TL;DR

This paper extends Foerster and modified Redfield theories to include the dynamics of quantum coherences, aligning well with exact numerical methods and sometimes outperforming standard Redfield results.

## Contribution

It derives formulas for coherences within these theories, overcoming a key limitation and improving accuracy in modeling excitation energy transfer.

## Key findings

- Formulas for coherences match hierarchical equations of motion results.
- Modified Redfield coherence formulas can outperform standard Redfield.
- Enhanced theoretical framework improves understanding of energy transfer dynamics.

## Abstract

Foerster and modified Redfield theories play one of the central roles in the description of excitation energy transfer in molecular systems. However, in the present state, these theories describe only the dynamics of populations of local electronic excitations or delocalized exciton eigenstates, respectively, i.e., the diagonal elements of the density matrix in the corresponding representation. They do not give prescription for propagating the off-diagonal elements of the density matrix (coherences). This is commonly accepted as a limitation of these theories. Here we derive formulas for the dynamics of the coherences in the framework of Foerster and modified Redfield theories and, thus, remove this limitation. These formulas provide excellent correspondence with numerically exact calculations according to the hierarchical equations of motion. Also we show that, even within the range of applicability of the standard Redfield theory, the formulas for coherences derived in the framework of the modified Redfield theory provide, in some cases, more precise results.