An efficient tool to calculate two-dimensional optical spectra for photoactive molecular complexes

TL;DR

This paper introduces a combined computational approach using CMRT and PMA to efficiently calculate two-dimensional optical spectra of photoactive complexes, balancing accuracy and computational cost.

Contribution

It develops and validates a combined CMRT+PMA method for simulating 2D spectra, offering a practical alternative to exact methods for complex systems.

Findings

CMRT accurately predicts decay rates in population dynamics.

Combined CMRT+PMA agrees well with exact calculations at short times.

Differences arise at long times due to stationary state discrepancies.

Abstract

We combine the coherent modified Redfield theory (CMRT) with the equation of motion-phase matching approach (PMA) to calculate two-dimensional photon echo spectra for photoactive molecular complexes with an intermediate strength of the coupling to their environment. Both techniques are highly efficient, yet they involve approximations at different levels. By explicitly comparing with the numerically exact quasi-adiabatic path integral approach, we show for the Fenna-Matthews-Olson complex that the CMRT describes the decay rates in the population dynamics well, but final stationary populations and the oscillation frequencies differ slightly. In addition, we use the combined CMRT+PMA to calculate two-dimensional photon-echo spectra for a simple dimer model. We find excellent agreement with the exact path integral calculations at short waiting times where the dynamics is still coherent. For long waiting times, differences occur due to different final stationary states, specifically for strong system-bath coupling. For weak to intermediate system-bath couplings, which is most important for natural photosynthetic complexes, the combined CMRT+PMA gives reasonable results with acceptable computational efforts.