Self-consistent approach to the dynamics of excitation energy transfer in multichromophoric systems

TL;DR

This paper introduces a self-consistent Born approximation method for exciton energy transfer in multichromophoric systems, improving accuracy over traditional approaches and applicable to complex environments.

Contribution

It formulates a self-consistent approach in Liouville space to better model exciton dynamics, especially in strong coupling and complex environmental conditions.

Findings

Self-consistent Born approximation aligns well with hierarchical equations of motion.

Improves modeling of energy transfer in strong and slow environment regimes.

Reasonably describes exciton dynamics in realistic multichromophoric systems.

Abstract

Computationally tractable and reliable, albeit approximate, methods for studying exciton transport in molecular aggregates immersed in structured bosonic environments have been actively developed. Going beyond the lowest-order (Born) approximation for the memory kernel of the quantum master equation typically results in complicated and possibly divergent expressions. Starting from the memory kernel in the Born approximation, and recognizing the quantum master equation as the Dyson equation of Green's functions theory, we formulate the self-consistent Born approximation to resum the memory-kernel perturbation series in powers of the exciton--environment interaction. Our formulation is in the Liouville space and frequency domain and handles arbitrary exciton--environment spectral densities. In a molecular dimer coupled to an overdamped oscillator environment, we conclude that the self-consistent cycle significantly improves the Born-approximation energy-transfer dynamics. The dynamics in the self-consistent Born approximation agree well with the solutions of hierarchical equations of motion over a wide range of parameters, including the most challenging regimes of strong exciton--environment interactions, slow environments, and low temperatures. This is rationalized by the analytical considerations of coherence-dephasing dynamics in the pure-dephasing model. We find that the self-consistent Born approximation is good (poor) at describing energy transfer modulated by an underdamped vibration resonant (off-resonant) with the exciton energy gap. Nevertheless, it reasonably describes exciton dynamics in the seven-site model of the Fenna--Matthews--Olson complex in a realistic environment comprising both an overdamped continuum and underdamped vibrations.