Issue 6, 2024

Exciton dynamics from the mapping approach to surface hopping: comparison with Förster and Redfield theories

Abstract

We compare the recently introduced multi-state mapping approach to surface hopping (MASH) with the Förster and Redfield theories of excitation energy transfer. Whereas Förster theory relies on weak coupling between chromophores, and Redfield theory assumes the electronic excitations to be weakly coupled to fast chromophore vibrations, MASH is free from any perturbative or Markovian approximations. We illustrate this with an example application to the rate of energy transfer in a Frenkel-exciton dimer, showing that MASH interpolates correctly between the opposing regimes in which the Förster and Redfield results are reliable. We then compare the three methods for a realistic model of the Fenna–Matthews–Olson complex with a structured vibrational spectral density and static disorder in the excitation energies. In this case there are no exact results for comparison so we use MASH to assess the validity of Förster and Redfield theories. We find that Förster theory is the more accurate of the two on the picosecond timescale, as has been shown previously for a simpler model of this particular light-harvesting complex. We also explore various ways to sample the initial electronic state in MASH and find that they all give very similar results for exciton dynamics.

Graphical abstract: Exciton dynamics from the mapping approach to surface hopping: comparison with Förster and Redfield theories

Article information

Article type
Paper
Submitted
05 des. 2023
Accepted
03 jan. 2024
First published
13 jan. 2024
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2024,26, 4929-4938

Exciton dynamics from the mapping approach to surface hopping: comparison with Förster and Redfield theories

J. E. Runeson, T. P. Fay and D. E. Manolopoulos, Phys. Chem. Chem. Phys., 2024, 26, 4929 DOI: 10.1039/D3CP05926J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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