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dc.contributor.author
Pérez Sirkin, Yamila Anahí
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dc.contributor.author
Tagliazucchi, Mario Eugenio
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dc.date.available
2024-02-27T13:45:22Z
dc.date.issued
2023-04
dc.identifier.citation
Pérez Sirkin, Yamila Anahí; Tagliazucchi, Mario Eugenio; Revisiting the Mechanisms of Charge Transport in Solutions of Redox-Active Molecules Using Computer Simulations: When and Why Do Analytical Theories Fail?; American Chemical Society; Journal of Physical Chemistry B; 127; 13; 4-2023; 2968-2978
dc.identifier.issn
1520-6106
dc.identifier.uri
http://hdl.handle.net/11336/228608
dc.description.abstract
Understanding charge transport is essential for the development of energy-storage applications. This work introduces a new theoretical methodology to model diffusive charge transport in solutions of redox-active molecules by combining Langevin dynamics for the spatial degrees of freedom and a master-equation formalism to describe the electron-hopping events between redox molecules. The model is used to analyze the effects of the concentration of the redox molecules and the strength of the intermolecular interactions on the charge-transport mechanism. In the past, the rate of charge transport has been modeled with the analytical Dahms-Ruff equation; however, this is a mean-field equation, whose range of validity has not been tested with less approximate theories. We show that the Dahms-Ruff equation fails to quantitatively predict the diffusion coefficient for charge transport for large concentrations of the redox species and high bimolecular electron-transfer rates, i.e., the most relevant conditions for energy-storage applications. Under these conditions, the diffusion coefficient for charge transport obtained from simulations is larger than that predicted from the Dahm-Ruff equation because of the formation of transient clusters of redox molecules. Also, intermolecular interactions, which are not taken into account by the Dahms-Ruff equation, play a central role in the charge transport of redox species. We show that the apparent diffusion coefficient experiences a maximum with respect to the strength of the intermolecular attractions. This maximum is traced back to the formation of clusters and their two opposite effects on the diffusion coefficient: electron hopping is fast within a cluster but inefficient between neighboring clusters.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
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dc.rights
info:eu-repo/semantics/restrictedAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
TRANSPORT
dc.subject
ENERGY
dc.subject
REDOX
dc.subject.classification
Físico-Química, Ciencia de los Polímeros, Electroquímica
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dc.subject.classification
Ciencias Químicas
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dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
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dc.title
Revisiting the Mechanisms of Charge Transport in Solutions of Redox-Active Molecules Using Computer Simulations: When and Why Do Analytical Theories Fail?
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2024-02-26T10:54:56Z
dc.journal.volume
127
dc.journal.number
13
dc.journal.pagination
2968-2978
dc.journal.pais
Estados Unidos
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dc.description.fil
Fil: Pérez Sirkin, Yamila Anahí. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
dc.description.fil
Fil: Tagliazucchi, Mario Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
dc.journal.title
Journal of Physical Chemistry B
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dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jpcb.2c06956
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/acs.jpcb.2c06956
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