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Title: Dynamics of charge transfer: Rate processes formulated with nonequilibrium Green's functions

Abstract

The authors examine the connection between electron transport under bias in a junction and nonadiabatic intramolecular electron transfer (ET). It is shown that under certain assumptions it is possible to define a stationary current that allows the computation of the intramolecular transfer rate using the same formalism that is employed in the description of transport. They show that the nonequilibrium Green's function formalism of quantum transport can be used to calculate the ET rate. The formal connection between electron transport and electron transfer is made, and they work out the simple case of an electronic level coupled to a vibrational mode representing a thermal bath and show that the result is the same as expected from a Fermi golden rule treatment, and in the high-temperature limit yields the Marcus electron transfer theory. The usefulness of this alternative formulation of rates is discussed.

Authors:
; ;  [1]
  1. Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113 and Center for Nanofabrication and Molecular Self Assembly, Northwestern University, Evanston, Illinois 60208-3113 (United States)
Publication Date:
OSTI Identifier:
20991252
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 126; Journal Issue: 16; Other Information: DOI: 10.1063/1.2735606; (c) 2007 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; CALCULATION METHODS; CHARGED-PARTICLE TRANSPORT; ELECTRON TRANSFER; ELECTRONIC STRUCTURE; ELECTRONS; GREEN FUNCTION; REACTION KINETICS

Citation Formats

Yeganeh, Sina, Ratner, Mark A, Mujica, Vladimiro, Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113, Center for Nanofabrication and Molecular Self Assembly, Northwestern University, Evanston, Illinois 60208-3113, Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439-4831, and Universidad Central de Venezuela, Facultad de Ciencias, Escuela de Quimica, Apartado 47102, Caraccas 1020-A. Dynamics of charge transfer: Rate processes formulated with nonequilibrium Green's functions. United States: N. p., 2007. Web. doi:10.1063/1.2735606.
Yeganeh, Sina, Ratner, Mark A, Mujica, Vladimiro, Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113, Center for Nanofabrication and Molecular Self Assembly, Northwestern University, Evanston, Illinois 60208-3113, Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439-4831, & Universidad Central de Venezuela, Facultad de Ciencias, Escuela de Quimica, Apartado 47102, Caraccas 1020-A. Dynamics of charge transfer: Rate processes formulated with nonequilibrium Green's functions. United States. https://doi.org/10.1063/1.2735606
Yeganeh, Sina, Ratner, Mark A, Mujica, Vladimiro, Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113, Center for Nanofabrication and Molecular Self Assembly, Northwestern University, Evanston, Illinois 60208-3113, Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439-4831, and Universidad Central de Venezuela, Facultad de Ciencias, Escuela de Quimica, Apartado 47102, Caraccas 1020-A. Sat . "Dynamics of charge transfer: Rate processes formulated with nonequilibrium Green's functions". United States. https://doi.org/10.1063/1.2735606.
@article{osti_20991252,
title = {Dynamics of charge transfer: Rate processes formulated with nonequilibrium Green's functions},
author = {Yeganeh, Sina and Ratner, Mark A and Mujica, Vladimiro and Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113 and Center for Nanofabrication and Molecular Self Assembly, Northwestern University, Evanston, Illinois 60208-3113 and Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439-4831 and Universidad Central de Venezuela, Facultad de Ciencias, Escuela de Quimica, Apartado 47102, Caraccas 1020-A},
abstractNote = {The authors examine the connection between electron transport under bias in a junction and nonadiabatic intramolecular electron transfer (ET). It is shown that under certain assumptions it is possible to define a stationary current that allows the computation of the intramolecular transfer rate using the same formalism that is employed in the description of transport. They show that the nonequilibrium Green's function formalism of quantum transport can be used to calculate the ET rate. The formal connection between electron transport and electron transfer is made, and they work out the simple case of an electronic level coupled to a vibrational mode representing a thermal bath and show that the result is the same as expected from a Fermi golden rule treatment, and in the high-temperature limit yields the Marcus electron transfer theory. The usefulness of this alternative formulation of rates is discussed.},
doi = {10.1063/1.2735606},
url = {https://www.osti.gov/biblio/20991252}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 16,
volume = 126,
place = {United States},
year = {2007},
month = {4}
}