Redfield Treatment of Multipathway Electron Transfer in Artificial Photosynthetic Systems

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Coherence effects on electron transfer in a series of symmetric and asymmetric two-, three-, four-, and five-site molecular model systems for photosystem I in cyanobacteria and green plants were studied. The total site energies of the electronic Hamiltonian were calculated using the density functional theory (DFT) formalism and included the zero point vibrational energies of the electron donors and acceptors. Site energies and couplings were calculated using a polarizable continuum model to represent various solvent environments, and the site-to-site couplings were calculated using fragment charge difference methods at the DFT level of theory. The Redfield formalism was used to propagate the electron density from the donors to the acceptors, incorporating relaxation and dephasing effects to describe the electron transfer processes. Changing the relative energies of the donor, intermediate acceptor, and final acceptor molecules in these assemblies has profound effects on the electron transfer rates as well as on the amplitude of the quantum oscillations observed. Increasing the ratio of a particular energy gap to the electronic coupling for a given pair of states leads to weaker quantum oscillations between sites. Biasing the intermediate acceptor energies to slightly favor one pathway leads to a general decrease in electron transfer yield.

Original languageEnglish
Pages (from-to)7190-7203
Number of pages14
JournalJournal of Physical Chemistry B
Volume121
Issue number29
DOIs
Publication statusPublished - Jul 27 2017

Fingerprint

electron transfer
Electrons
Density functional theory
energy
density functional theory
formalism
Photosystem I Protein Complex
Hamiltonians
oscillations
electronics
assemblies
Carrier concentration
Energy gap
fragments
continuums
Molecules
molecules
electrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Redfield Treatment of Multipathway Electron Transfer in Artificial Photosynthetic Systems. / Powell, Daniel D.; Wasielewski, Michael R; Ratner, Mark A.

In: Journal of Physical Chemistry B, Vol. 121, No. 29, 27.07.2017, p. 7190-7203.

Research output: Contribution to journalArticle

@article{2a641c04f1584e9099a0e028b886b3fd,
title = "Redfield Treatment of Multipathway Electron Transfer in Artificial Photosynthetic Systems",
abstract = "Coherence effects on electron transfer in a series of symmetric and asymmetric two-, three-, four-, and five-site molecular model systems for photosystem I in cyanobacteria and green plants were studied. The total site energies of the electronic Hamiltonian were calculated using the density functional theory (DFT) formalism and included the zero point vibrational energies of the electron donors and acceptors. Site energies and couplings were calculated using a polarizable continuum model to represent various solvent environments, and the site-to-site couplings were calculated using fragment charge difference methods at the DFT level of theory. The Redfield formalism was used to propagate the electron density from the donors to the acceptors, incorporating relaxation and dephasing effects to describe the electron transfer processes. Changing the relative energies of the donor, intermediate acceptor, and final acceptor molecules in these assemblies has profound effects on the electron transfer rates as well as on the amplitude of the quantum oscillations observed. Increasing the ratio of a particular energy gap to the electronic coupling for a given pair of states leads to weaker quantum oscillations between sites. Biasing the intermediate acceptor energies to slightly favor one pathway leads to a general decrease in electron transfer yield.",
author = "Powell, {Daniel D.} and Wasielewski, {Michael R} and Ratner, {Mark A}",
year = "2017",
month = "7",
day = "27",
doi = "10.1021/acs.jpcb.7b02748",
language = "English",
volume = "121",
pages = "7190--7203",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "29",

}

TY - JOUR

T1 - Redfield Treatment of Multipathway Electron Transfer in Artificial Photosynthetic Systems

AU - Powell, Daniel D.

AU - Wasielewski, Michael R

AU - Ratner, Mark A

PY - 2017/7/27

Y1 - 2017/7/27

N2 - Coherence effects on electron transfer in a series of symmetric and asymmetric two-, three-, four-, and five-site molecular model systems for photosystem I in cyanobacteria and green plants were studied. The total site energies of the electronic Hamiltonian were calculated using the density functional theory (DFT) formalism and included the zero point vibrational energies of the electron donors and acceptors. Site energies and couplings were calculated using a polarizable continuum model to represent various solvent environments, and the site-to-site couplings were calculated using fragment charge difference methods at the DFT level of theory. The Redfield formalism was used to propagate the electron density from the donors to the acceptors, incorporating relaxation and dephasing effects to describe the electron transfer processes. Changing the relative energies of the donor, intermediate acceptor, and final acceptor molecules in these assemblies has profound effects on the electron transfer rates as well as on the amplitude of the quantum oscillations observed. Increasing the ratio of a particular energy gap to the electronic coupling for a given pair of states leads to weaker quantum oscillations between sites. Biasing the intermediate acceptor energies to slightly favor one pathway leads to a general decrease in electron transfer yield.

AB - Coherence effects on electron transfer in a series of symmetric and asymmetric two-, three-, four-, and five-site molecular model systems for photosystem I in cyanobacteria and green plants were studied. The total site energies of the electronic Hamiltonian were calculated using the density functional theory (DFT) formalism and included the zero point vibrational energies of the electron donors and acceptors. Site energies and couplings were calculated using a polarizable continuum model to represent various solvent environments, and the site-to-site couplings were calculated using fragment charge difference methods at the DFT level of theory. The Redfield formalism was used to propagate the electron density from the donors to the acceptors, incorporating relaxation and dephasing effects to describe the electron transfer processes. Changing the relative energies of the donor, intermediate acceptor, and final acceptor molecules in these assemblies has profound effects on the electron transfer rates as well as on the amplitude of the quantum oscillations observed. Increasing the ratio of a particular energy gap to the electronic coupling for a given pair of states leads to weaker quantum oscillations between sites. Biasing the intermediate acceptor energies to slightly favor one pathway leads to a general decrease in electron transfer yield.

UR - http://www.scopus.com/inward/record.url?scp=85026547285&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85026547285&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcb.7b02748

DO - 10.1021/acs.jpcb.7b02748

M3 - Article

C2 - 28661144

AN - SCOPUS:85026547285

VL - 121

SP - 7190

EP - 7203

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 29

ER -