Modeling the free energy surfaces of electron transfer in condensed phases

Dmitry Matyushov, Gregory A. Voth

Research output: Contribution to journalArticle

71 Citations (Scopus)

Abstract

A three parameter model for the free energy surfaces of electron transfer (ET) in condensed phases was presented. This model is based on the Hamiltonian of a two-state solute linearly coupled to a harmonic, classical solvent mode with different force constants in the initial and final states. It extends the two parameter Marcus-Hush model by introducing the third parameter α1 reflecting the variation of the force constant of the classical solvent mode driving ET. Its validity is equivalent to the condition of thermodynamic stability of the driving solvent mode. The model parameters are fully defined by the first two equilibrium cumulants of the ET reaction coordinate.

Original languageEnglish (US)
Pages (from-to)5413-5423
Number of pages11
JournalJournal of Chemical Physics
Volume113
Issue number13
DOIs
StatePublished - Oct 1 2000

Fingerprint

Free energy
electron transfer
free energy
Electrons
Hamiltonians
solutes
Thermodynamic stability
harmonics
thermodynamics

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Modeling the free energy surfaces of electron transfer in condensed phases. / Matyushov, Dmitry; Voth, Gregory A.

In: Journal of Chemical Physics, Vol. 113, No. 13, 01.10.2000, p. 5413-5423.

Research output: Contribution to journalArticle

@article{05ad2310927c4565ab61317bf15a4140,
title = "Modeling the free energy surfaces of electron transfer in condensed phases",
abstract = "A three parameter model for the free energy surfaces of electron transfer (ET) in condensed phases was presented. This model is based on the Hamiltonian of a two-state solute linearly coupled to a harmonic, classical solvent mode with different force constants in the initial and final states. It extends the two parameter Marcus-Hush model by introducing the third parameter α1 reflecting the variation of the force constant of the classical solvent mode driving ET. Its validity is equivalent to the condition of thermodynamic stability of the driving solvent mode. The model parameters are fully defined by the first two equilibrium cumulants of the ET reaction coordinate.",
author = "Dmitry Matyushov and Voth, {Gregory A.}",
year = "2000",
month = "10",
day = "1",
doi = "10.1063/1.1289886",
language = "English (US)",
volume = "113",
pages = "5413--5423",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "13",

}

TY - JOUR

T1 - Modeling the free energy surfaces of electron transfer in condensed phases

AU - Matyushov, Dmitry

AU - Voth, Gregory A.

PY - 2000/10/1

Y1 - 2000/10/1

N2 - A three parameter model for the free energy surfaces of electron transfer (ET) in condensed phases was presented. This model is based on the Hamiltonian of a two-state solute linearly coupled to a harmonic, classical solvent mode with different force constants in the initial and final states. It extends the two parameter Marcus-Hush model by introducing the third parameter α1 reflecting the variation of the force constant of the classical solvent mode driving ET. Its validity is equivalent to the condition of thermodynamic stability of the driving solvent mode. The model parameters are fully defined by the first two equilibrium cumulants of the ET reaction coordinate.

AB - A three parameter model for the free energy surfaces of electron transfer (ET) in condensed phases was presented. This model is based on the Hamiltonian of a two-state solute linearly coupled to a harmonic, classical solvent mode with different force constants in the initial and final states. It extends the two parameter Marcus-Hush model by introducing the third parameter α1 reflecting the variation of the force constant of the classical solvent mode driving ET. Its validity is equivalent to the condition of thermodynamic stability of the driving solvent mode. The model parameters are fully defined by the first two equilibrium cumulants of the ET reaction coordinate.

UR - http://www.scopus.com/inward/record.url?scp=0034299526&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0034299526&partnerID=8YFLogxK

U2 - 10.1063/1.1289886

DO - 10.1063/1.1289886

M3 - Article

AN - SCOPUS:0034299526

VL - 113

SP - 5413

EP - 5423

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 13

ER -