Nuclear quantum effects slow down the energy transfer in biological light-harvesting complexes

TL;DR

This study investigates how nuclear quantum effects influence excitation energy transfer in biological light-harvesting complexes, revealing that quantum effects slow down transfer rates, especially in systems with large energy gaps and strong vibronic coupling.

Contribution

The paper introduces a variational polaron approach to incorporate nuclear quantum effects into a mixed quantum-classical framework, validated against quantum benchmarks and applied to key biological complexes.

Findings

Quantum effects delay energy transfer in light-harvesting complexes.

Classical treatment accurately reproduces long-term populations.

Quantum effects significantly slow transfer in systems with large energy gaps.

Abstract

We assess how quantum-mechanical effects associated with high-frequency chromophore vibrations influence excitation energy transfer in biological light-harvesting complexes. We begin with a mixed quantum-classical theory that combines a quantum description of the electronic motion with a classical description of the nuclear motion in a way that is consistent with the quantum-classical equilibrium distribution. We then include nuclear quantum effects in this theory with a variational polaron transformation of the high frequency vibrational modes. This approach is validated by comparison with fully quantum mechanical benchmark calculations and then applied to three prototypical biological light-harvesting complexes. We find that high-frequency vibrations delay the energy transfer in the quantum treatment, but accelerate it in the classical treatment. For the inter-ring transfer in the light-harvesting complex 2 of purple bacteria, the transfer rate is a factor of 1.5 times slower in the quantum treatment than the classical. The transfer timescale in the Fenna--Matthews--Olson complex is essentially the same in both cases, whereas the transfer in light-harvesting complex II of spinach is 1.7 times slower in the quantum treatment. In all cases, the quantum mechanical long-time equilibrium populations of the chromophores are well reproduced by the classical treatment, suggesting that nuclear quantum effects are generally unimportant for the directionality of energy transfer. Nuclear quantum effects do however reduce the transfer rate in systems with large excitonic energy gaps and strong vibronic coupling to high-frequency vibrational modes.