Combining molecular dynamics and ab initio quantum-chemistry to describe electron transfer reactions in electrochemical environments

A theoretical model is presented aimed to provide a detailed microscopic description of the electron transfer reaction in an electrochemical environment. The present approach is based on the well-known two state model extended by the novelty that the energy of the two states involved in the electron...

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Autores: Domínguez-Ariza, David, Hartnig, Christoph, Sousa Romero, Carmen, Illas i Riera, Francesc
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2004
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/150637
Acceso en línea:https://hdl.handle.net/2445/150637
Access Level:acceso abierto
Palabra clave:Dinàmica molecular
Química quàntica
Electroestàtica
Molecular dynamics
Quantum chemistry
Electrostatics
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spelling Combining molecular dynamics and ab initio quantum-chemistry to describe electron transfer reactions in electrochemical environmentsDomínguez-Ariza, DavidHartnig, ChristophSousa Romero, CarmenIllas i Riera, FrancescDinàmica molecularQuímica quànticaElectroestàticaMolecular dynamicsQuantum chemistryElectrostaticsA theoretical model is presented aimed to provide a detailed microscopic description of the electron transfer reaction in an electrochemical environment. The present approach is based on the well-known two state model extended by the novelty that the energy of the two states involved in the electron transfer reaction is computed quantum mechanically as a function of the solvent coordinate, as defined in the Marcus theory, and of the intensity of an external electric field. The solvent conformations defining the reaction coordinate are obtained from classical molecular dynamics and then transferred to the quantum mechanical model. The overall approach has been applied to the electron transfer between a chloride anion and a single crystal Cu(100) electrode. It is found that the solvent exerts a strong influence on the equilibrium geometry of the halide and hence on the relative energy of the two states involved in the electron transfer reaction. Finally, both solvent fluctuations and external field facilitate the electron transfer although solvent effects have a stronger influence.American Institute of Physics2004info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://hdl.handle.net/2445/150637Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésReproducció del document publicat a: https://doi.org/10.1063/1.1760071Journal of Chemical Physics, 2004, vol. 121, num. 2, p. 1066-1073https://doi.org/10.1063/1.1760071(c) American Institute of Physics , 2004info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1506372026-05-27T06:46:51Z
dc.title.none.fl_str_mv Combining molecular dynamics and ab initio quantum-chemistry to describe electron transfer reactions in electrochemical environments
title Combining molecular dynamics and ab initio quantum-chemistry to describe electron transfer reactions in electrochemical environments
spellingShingle Combining molecular dynamics and ab initio quantum-chemistry to describe electron transfer reactions in electrochemical environments
Domínguez-Ariza, David
Dinàmica molecular
Química quàntica
Electroestàtica
Molecular dynamics
Quantum chemistry
Electrostatics
title_short Combining molecular dynamics and ab initio quantum-chemistry to describe electron transfer reactions in electrochemical environments
title_full Combining molecular dynamics and ab initio quantum-chemistry to describe electron transfer reactions in electrochemical environments
title_fullStr Combining molecular dynamics and ab initio quantum-chemistry to describe electron transfer reactions in electrochemical environments
title_full_unstemmed Combining molecular dynamics and ab initio quantum-chemistry to describe electron transfer reactions in electrochemical environments
title_sort Combining molecular dynamics and ab initio quantum-chemistry to describe electron transfer reactions in electrochemical environments
dc.creator.none.fl_str_mv Domínguez-Ariza, David
Hartnig, Christoph
Sousa Romero, Carmen
Illas i Riera, Francesc
author Domínguez-Ariza, David
author_facet Domínguez-Ariza, David
Hartnig, Christoph
Sousa Romero, Carmen
Illas i Riera, Francesc
author_role author
author2 Hartnig, Christoph
Sousa Romero, Carmen
Illas i Riera, Francesc
author2_role author
author
author
dc.subject.none.fl_str_mv Dinàmica molecular
Química quàntica
Electroestàtica
Molecular dynamics
Quantum chemistry
Electrostatics
topic Dinàmica molecular
Química quàntica
Electroestàtica
Molecular dynamics
Quantum chemistry
Electrostatics
description A theoretical model is presented aimed to provide a detailed microscopic description of the electron transfer reaction in an electrochemical environment. The present approach is based on the well-known two state model extended by the novelty that the energy of the two states involved in the electron transfer reaction is computed quantum mechanically as a function of the solvent coordinate, as defined in the Marcus theory, and of the intensity of an external electric field. The solvent conformations defining the reaction coordinate are obtained from classical molecular dynamics and then transferred to the quantum mechanical model. The overall approach has been applied to the electron transfer between a chloride anion and a single crystal Cu(100) electrode. It is found that the solvent exerts a strong influence on the equilibrium geometry of the halide and hence on the relative energy of the two states involved in the electron transfer reaction. Finally, both solvent fluctuations and external field facilitate the electron transfer although solvent effects have a stronger influence.
publishDate 2004
dc.date.none.fl_str_mv 2004
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/150637
url https://hdl.handle.net/2445/150637
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Reproducció del document publicat a: https://doi.org/10.1063/1.1760071
Journal of Chemical Physics, 2004, vol. 121, num. 2, p. 1066-1073
https://doi.org/10.1063/1.1760071
dc.rights.none.fl_str_mv (c) American Institute of Physics , 2004
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) American Institute of Physics , 2004
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Institute of Physics
publisher.none.fl_str_mv American Institute of Physics
dc.source.none.fl_str_mv Articles publicats en revistes (Ciència dels Materials i Química Física)
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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