Monte Carlo simulations and mean-field modeling of electric double layers at weakly and moderately charged spherical macroions
Autor(a) principal: | |
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Data de Publicação: | 2021 |
Outros Autores: | , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1103/PhysRevE.104.034609 http://hdl.handle.net/11449/222528 |
Resumo: | Monte Carlo simulations are employed to determine the differential capacitance of an electric double layer formed by small size-symmetric anions and cations in the vicinity of weakly to moderately charged macroions. The influence of interfacial curvature is deduced by investigating spherical macroions, ranging from flat to moderately curved. We also calculate the differential capacitance using a previously developed mean-field model where, in addition to electrostatic interactions, the excluded volumes of the ions are taken into account using either the lattice-gas or the Carnahan-Starling equation of state. For both equations of state, we compare the mean-field model for arbitrary curvature with a recently developed second-order curvature expansion. Our Monte Carlo simulations predict an increase in the differential capacitance with growing macroion curvature if the surface charge density is small, whereas for moderately charged macroions the differential capacitance passes through a local minimum. Both mean-field models tend to somewhat overestimate the differential capacitance as compared with Monte Carlo simulations. At the same time, they do reproduce the curvature dependence of the differential capacitance, especially for small surface charge density. Our study suggests that the quality of mean-field modeling does not worsen when weakly or moderately charged macroions exhibit spherical curvature. |
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Monte Carlo simulations and mean-field modeling of electric double layers at weakly and moderately charged spherical macroionsMonte Carlo simulations are employed to determine the differential capacitance of an electric double layer formed by small size-symmetric anions and cations in the vicinity of weakly to moderately charged macroions. The influence of interfacial curvature is deduced by investigating spherical macroions, ranging from flat to moderately curved. We also calculate the differential capacitance using a previously developed mean-field model where, in addition to electrostatic interactions, the excluded volumes of the ions are taken into account using either the lattice-gas or the Carnahan-Starling equation of state. For both equations of state, we compare the mean-field model for arbitrary curvature with a recently developed second-order curvature expansion. Our Monte Carlo simulations predict an increase in the differential capacitance with growing macroion curvature if the surface charge density is small, whereas for moderately charged macroions the differential capacitance passes through a local minimum. Both mean-field models tend to somewhat overestimate the differential capacitance as compared with Monte Carlo simulations. At the same time, they do reproduce the curvature dependence of the differential capacitance, especially for small surface charge density. Our study suggests that the quality of mean-field modeling does not worsen when weakly or moderately charged macroions exhibit spherical curvature.Institute of Chemistry State University of Campinas (UNICAMP), São PauloCenter for Computational Engineering and Sciences State University of Campinas (UNICAMP), São PauloDepartment of Physics São Paulo State University (UNESP) Institute of Biosciences Humanities and Exact Sciences, São PauloDepartment of Physics North Dakota State UniversityDepartment of Physics São Paulo State University (UNESP) Institute of Biosciences Humanities and Exact Sciences, São PauloUniversidade Estadual de Campinas (UNICAMP)Universidade Estadual Paulista (UNESP)North Dakota State UniversityCaetano, Daniel L. Z.De Carvalho, Sidney J. [UNESP]Bossa, Guilherme V. [UNESP]May, Sylvio2022-04-28T19:45:17Z2022-04-28T19:45:17Z2021-09-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://dx.doi.org/10.1103/PhysRevE.104.034609Physical Review E, v. 104, n. 3, 2021.2470-00532470-0045http://hdl.handle.net/11449/22252810.1103/PhysRevE.104.0346092-s2.0-85116018702Scopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengPhysical Review Einfo:eu-repo/semantics/openAccess2022-04-28T19:45:17Zoai:repositorio.unesp.br:11449/222528Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T14:38:28.467514Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Monte Carlo simulations and mean-field modeling of electric double layers at weakly and moderately charged spherical macroions |
title |
Monte Carlo simulations and mean-field modeling of electric double layers at weakly and moderately charged spherical macroions |
spellingShingle |
Monte Carlo simulations and mean-field modeling of electric double layers at weakly and moderately charged spherical macroions Caetano, Daniel L. Z. |
title_short |
Monte Carlo simulations and mean-field modeling of electric double layers at weakly and moderately charged spherical macroions |
title_full |
Monte Carlo simulations and mean-field modeling of electric double layers at weakly and moderately charged spherical macroions |
title_fullStr |
Monte Carlo simulations and mean-field modeling of electric double layers at weakly and moderately charged spherical macroions |
title_full_unstemmed |
Monte Carlo simulations and mean-field modeling of electric double layers at weakly and moderately charged spherical macroions |
title_sort |
Monte Carlo simulations and mean-field modeling of electric double layers at weakly and moderately charged spherical macroions |
author |
Caetano, Daniel L. Z. |
author_facet |
Caetano, Daniel L. Z. De Carvalho, Sidney J. [UNESP] Bossa, Guilherme V. [UNESP] May, Sylvio |
author_role |
author |
author2 |
De Carvalho, Sidney J. [UNESP] Bossa, Guilherme V. [UNESP] May, Sylvio |
author2_role |
author author author |
dc.contributor.none.fl_str_mv |
Universidade Estadual de Campinas (UNICAMP) Universidade Estadual Paulista (UNESP) North Dakota State University |
dc.contributor.author.fl_str_mv |
Caetano, Daniel L. Z. De Carvalho, Sidney J. [UNESP] Bossa, Guilherme V. [UNESP] May, Sylvio |
description |
Monte Carlo simulations are employed to determine the differential capacitance of an electric double layer formed by small size-symmetric anions and cations in the vicinity of weakly to moderately charged macroions. The influence of interfacial curvature is deduced by investigating spherical macroions, ranging from flat to moderately curved. We also calculate the differential capacitance using a previously developed mean-field model where, in addition to electrostatic interactions, the excluded volumes of the ions are taken into account using either the lattice-gas or the Carnahan-Starling equation of state. For both equations of state, we compare the mean-field model for arbitrary curvature with a recently developed second-order curvature expansion. Our Monte Carlo simulations predict an increase in the differential capacitance with growing macroion curvature if the surface charge density is small, whereas for moderately charged macroions the differential capacitance passes through a local minimum. Both mean-field models tend to somewhat overestimate the differential capacitance as compared with Monte Carlo simulations. At the same time, they do reproduce the curvature dependence of the differential capacitance, especially for small surface charge density. Our study suggests that the quality of mean-field modeling does not worsen when weakly or moderately charged macroions exhibit spherical curvature. |
publishDate |
2021 |
dc.date.none.fl_str_mv |
2021-09-01 2022-04-28T19:45:17Z 2022-04-28T19:45:17Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://dx.doi.org/10.1103/PhysRevE.104.034609 Physical Review E, v. 104, n. 3, 2021. 2470-0053 2470-0045 http://hdl.handle.net/11449/222528 10.1103/PhysRevE.104.034609 2-s2.0-85116018702 |
url |
http://dx.doi.org/10.1103/PhysRevE.104.034609 http://hdl.handle.net/11449/222528 |
identifier_str_mv |
Physical Review E, v. 104, n. 3, 2021. 2470-0053 2470-0045 10.1103/PhysRevE.104.034609 2-s2.0-85116018702 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Physical Review E |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.source.none.fl_str_mv |
Scopus reponame:Repositório Institucional da UNESP instname:Universidade Estadual Paulista (UNESP) instacron:UNESP |
instname_str |
Universidade Estadual Paulista (UNESP) |
instacron_str |
UNESP |
institution |
UNESP |
reponame_str |
Repositório Institucional da UNESP |
collection |
Repositório Institucional da UNESP |
repository.name.fl_str_mv |
Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP) |
repository.mail.fl_str_mv |
|
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1808128393526378496 |