Photon correlation time-asymmetry and dynamical coherence in multichromophoric systems

TL;DR

This paper demonstrates that polarization-filtered two-photon correlations can reveal quantum coherence and transport mechanisms in multichromophoric systems like the FMO complex, surpassing classical bounds and providing new insights into excitation dynamics.

Contribution

It introduces a novel method using photon correlation asymmetry to probe quantum coherence in biomolecular aggregates under realistic conditions.

Findings

FMO violates classical correlation asymmetry bounds

Photon correlation asymmetry relates to population-coherence transfer

Method can detect quantum coherence in steady-state conditions

Abstract

We theoretically investigate polarization-filtered two-photon correlations for the light emitted by a multichromophoric system undergoing excitation transport under realistic exciton-phonon interactions, and subject to continuous incoherent illumination. We show that for a biomolecular aggregate, such as the Fenna-Matthews Olson (FMO) photosynthetic complex, time-asymmetries in the cross-correlations of photons corresponding to different polarizations can be exploited to probe both quantum coherent transport mechanisms and steady-state coherence properties, which are not witnessed by zero-delay correlations. A classical bound on correlation asymmetry is obtained, which FMO is shown to violate using exact numerical calculations. Our analysis indicates that the dominant contributions to time-asymmetry in such photon cross-correlations are population to coherence transfer for Frenkel-Exciton models. Our results therefore put forward photon correlation asymmetry as a promising approach to investigate coherent contributions to excited-stated dynamics in molecular aggregates and other many-site quantum emitters.