Dynamics of coherence, localization and excitation transfer in disordered nanorings

TL;DR

This study investigates how environmental phonons can enhance excitation transfer in disordered nanorings, revealing an optimal exciton-phonon coupling that reduces localization and promotes efficient energy transport in photosynthetic systems.

Contribution

It provides a comprehensive analysis of exciton dynamics in disordered nanorings, explicitly including nuclear motion and identifying conditions that optimize excitation transfer.

Findings

Optimal exciton-phonon coupling suppresses localization.

Environmental phonons facilitate energy relaxation to extended excitons.

Enhanced excitation transfer observed in LH2 system model.

Abstract

Self-assembled supramolecular aggregates are excellent candidates for the design of efficient excitation transport devices. Both artificially prepared and natural photosynthetic aggregates in plants and bacteria present an important degree of disorder that is supposed to hinder excitation transport. Besides, molecular excitations couple to nuclear motion affecting excitation transport in a variety of ways. We present an exhaustive study of exciton dynamics in disordered nanorings with long-range interactions under the influence of a phonon bath and take the LH2 system of purple bacteria as a model. Nuclear motion is explicitly taken into account by employing the Davydov ansatz description of the polaron and quantum dynamics are obtained using a time-dependent variational method. We reveal an optimal exciton-phonon coupling that suppresses disorder-induced localization and facilitate excitation de-trapping. This excitation transfer enhancement, mediated by environmental phonons, is attributed to energy relaxation toward extended, low-energy excitons provided by the precise LH2 geometry with anti-parallel dipoles and long-range interactions. An analysis of localization and spectral statistics is followed by dynamical measures of coherence and localization, transfer efficiency and superradiance. Linear absorption, 2D photon-echo spectra and diffusion measures of the exciton are examined to monitor the diffusive behavior as a function of the strengths of disorder and exciton-phonon coupling.