Possible Role of Interference and Sink Effects in Nonphotochemical Quenching in Photosynthetic Complexes

TL;DR

This paper presents a quantum model illustrating how interference and sink effects may regulate nonphotochemical quenching in light-harvesting complexes, potentially reducing damage during photosynthesis.

Contribution

The study introduces a novel quantum mathematical model incorporating interference and sink effects to explain NPQ mechanisms in photosynthetic complexes.

Findings

Quantum interference can suppress damaging pathways in NPQ.

Sink effects influence the efficiency of energy dissipation.

Model suggests ways to optimize artificial light-harvesting systems.

Abstract

We describe a simple and consistent quantum mathematical model that simulates the possible role of quantum interference and sink effects in the nonphotochemical quenching (NPQ) in light-harvesting complexes (LHCs). Our model consists of a network of five interconnected sites (excitonic states) responsible for the NPQ mechanism: (i) Two excited states of chlorophyll molecules, $ChlA^*$ and $ChlB^*$, forming an LHC dimer, which is initially populated; (ii) A "damaging" site which is responsible for production of singlet oxygen and other destructive outcomes; (iii) The $(ChlA-Zea)^*$ heterodimer excited state (Zea indicates zeaxanthin); and (iv) The charge transfer state of this heterodimer, $(ChlA^{-}-Zea^{+})^*$. In our model, both damaging and charge transfer states are described by discrete electron energy levels attached to their sinks, that mimic the continuum part of electron energy spectrum, as at these sites the electron participates in quasi-irreversible chemical reactions. All five excitonic sites interact with the protein environment that is modeled using a stochastic approach. As an example, we apply our model to demonstrate possible contributions of quantum interference and sink effects in the NPQ mechanism in the CP29 minor LHC. Our numerical results on the quantum dynamics of the reduced density matrix, demonstrate a possible way to significantly suppress, under some conditions, the damaging channel using quantum interference effects and sinks. The results demonstrate the possible role of interference and sink effects for modeling, engineering, and optimizing the performance of the NPQ processes in both natural and artificial light-harvesting complexes.