Modeling of excitation dynamics in photosynthetic light-harvesting complexes: exact versus perturbative approaches

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Abstract

We compare various theoretical approaches that are frequently used for modeling the excitation dynamics in photosynthetic light-harvesting complexes. As an example, we calculate the dynamics in the major light-harvesting complex from higher plants using the standard Redfield theory, the coherent modified Redfield theory combined with the generalized Forster theory, and the scaled hierarchical equation of motion (HEOM). The modified Redfield and coherent modified Redfield theories predict unrealistically fast transfers between weakly coupled and isoenergetic sites due to the secular character of these approaches. This shortcoming can be excluded by the artificial breaking of exciton mixing between these sites and invoking a generalized Forster theory to calculate the transfers between them. A critical cutoff indicating which exciton couplings should be broken is dependent on the energy gap between the corresponding sites (and therefore can be different for different parts of the complex). An adequate determination of the strongly coupled compartments of the whole complex allows us to obtain a quantitatively correct description with the combined Redfield-Forster approach, resulting in kinetics not much different from the exact HEOM solution.
Original languageEnglish
Article number124003
JournalJournal of Physics B: Atomic, Molecular and Optical Physics
Volume50
Issue number12
DOIs
Publication statusPublished - 28 Jun 2017

Keywords

  • photosynthesis
  • energy transfer
  • exciton
  • coherence
  • exciton-phonon coupling
  • light-harvesting antenna

Cite this

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title = "Modeling of excitation dynamics in photosynthetic light-harvesting complexes: exact versus perturbative approaches",
abstract = "We compare various theoretical approaches that are frequently used for modeling the excitation dynamics in photosynthetic light-harvesting complexes. As an example, we calculate the dynamics in the major light-harvesting complex from higher plants using the standard Redfield theory, the coherent modified Redfield theory combined with the generalized Forster theory, and the scaled hierarchical equation of motion (HEOM). The modified Redfield and coherent modified Redfield theories predict unrealistically fast transfers between weakly coupled and isoenergetic sites due to the secular character of these approaches. This shortcoming can be excluded by the artificial breaking of exciton mixing between these sites and invoking a generalized Forster theory to calculate the transfers between them. A critical cutoff indicating which exciton couplings should be broken is dependent on the energy gap between the corresponding sites (and therefore can be different for different parts of the complex). An adequate determination of the strongly coupled compartments of the whole complex allows us to obtain a quantitatively correct description with the combined Redfield-Forster approach, resulting in kinetics not much different from the exact HEOM solution.",
keywords = "photosynthesis, energy transfer, exciton, coherence, exciton-phonon coupling, light-harvesting antenna",
author = "Novoderezhkin, {Vladimir I.} and {van Grondelle}, Rienk",
year = "2017",
month = "6",
day = "28",
doi = "10.1088/1361-6455/aa6b87",
language = "English",
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journal = "Journal of Physics B: Atomic, Molecular and Optical Physics",
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TY - JOUR

T1 - Modeling of excitation dynamics in photosynthetic light-harvesting complexes: exact versus perturbative approaches

AU - Novoderezhkin, Vladimir I.

AU - van Grondelle, Rienk

PY - 2017/6/28

Y1 - 2017/6/28

N2 - We compare various theoretical approaches that are frequently used for modeling the excitation dynamics in photosynthetic light-harvesting complexes. As an example, we calculate the dynamics in the major light-harvesting complex from higher plants using the standard Redfield theory, the coherent modified Redfield theory combined with the generalized Forster theory, and the scaled hierarchical equation of motion (HEOM). The modified Redfield and coherent modified Redfield theories predict unrealistically fast transfers between weakly coupled and isoenergetic sites due to the secular character of these approaches. This shortcoming can be excluded by the artificial breaking of exciton mixing between these sites and invoking a generalized Forster theory to calculate the transfers between them. A critical cutoff indicating which exciton couplings should be broken is dependent on the energy gap between the corresponding sites (and therefore can be different for different parts of the complex). An adequate determination of the strongly coupled compartments of the whole complex allows us to obtain a quantitatively correct description with the combined Redfield-Forster approach, resulting in kinetics not much different from the exact HEOM solution.

AB - We compare various theoretical approaches that are frequently used for modeling the excitation dynamics in photosynthetic light-harvesting complexes. As an example, we calculate the dynamics in the major light-harvesting complex from higher plants using the standard Redfield theory, the coherent modified Redfield theory combined with the generalized Forster theory, and the scaled hierarchical equation of motion (HEOM). The modified Redfield and coherent modified Redfield theories predict unrealistically fast transfers between weakly coupled and isoenergetic sites due to the secular character of these approaches. This shortcoming can be excluded by the artificial breaking of exciton mixing between these sites and invoking a generalized Forster theory to calculate the transfers between them. A critical cutoff indicating which exciton couplings should be broken is dependent on the energy gap between the corresponding sites (and therefore can be different for different parts of the complex). An adequate determination of the strongly coupled compartments of the whole complex allows us to obtain a quantitatively correct description with the combined Redfield-Forster approach, resulting in kinetics not much different from the exact HEOM solution.

KW - photosynthesis

KW - energy transfer

KW - exciton

KW - coherence

KW - exciton-phonon coupling

KW - light-harvesting antenna

U2 - 10.1088/1361-6455/aa6b87

DO - 10.1088/1361-6455/aa6b87

M3 - Article

VL - 50

JO - Journal of Physics B: Atomic, Molecular and Optical Physics

JF - Journal of Physics B: Atomic, Molecular and Optical Physics

SN - 0953-4075

IS - 12

M1 - 124003

ER -