Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulations

Autores
Pinto, Oscar Alejandro; Nieto Quintas, Felix Daniel; Ramirez Pastor, Antonio Jose
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The statistical thermodynamics of straight rigid rods of length k (k-mers) with nonadditive lateral interactions was developed on a generalization in the spirit of the lattice-gas model and the classical Bragg-Williams approximation (BWA) and the quasichemical approximation (QCA). The new theoretical framework is obtained by combining (i) the exact analytical expression for the partition function of noninteracting linear k-mers adsorbed in one dimension and its extension to higher dimensions, and (ii) a generalization of BWA and QCA in which the adsorbate can occupy more than one adsorption site. The traditional assumption of a strictly pairwise additive nearest-neighbors interaction is replaced by a more general one, namely that the bond linking a certain atom with any of its neighbors depends considerably on how many of them are actually present (or absent) on the sites in the first coordination shell of the atom. The coverage and temperature dependence of the Helmholtz free energy, chemical potential, configurational entropy, and differential heat of adsorption are given. The formalism (i) reproduces the classical results for monomers, (ii) leads to the exact statistical thermodynamics of nonadditive interacting k-mers adsorbed in one dimension, and (iii) provides a close approximation for two-dimensional systems, taking into account multisite occupancy and nonadditive lateral interactions. Comparisons with Monte Carlo simulations are performed in order to test the validity of the theoretical model. Significant quantitative differences are shown and discussed. In all cases, the QCA appears to be the more accurate approach.
Fil: Pinto, Oscar Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Física Aplicada; Argentina. Universidad Nacional de San Luis; Argentina
Fil: Nieto Quintas, Felix Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Física Aplicada; Argentina. Universidad Nacional de San Luis; Argentina
Fil: Ramirez Pastor, Antonio Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Física Aplicada; Argentina. Universidad Nacional de San Luis; Argentina
Materia
Thermodynamics
Nonadditive
Monte Carlo Simulations
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/14151
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulationsPinto, Oscar AlejandroNieto Quintas, Felix DanielRamirez Pastor, Antonio JoseThermodynamicsNonadditiveMonte Carlo Simulationshttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1The statistical thermodynamics of straight rigid rods of length k (k-mers) with nonadditive lateral interactions was developed on a generalization in the spirit of the lattice-gas model and the classical Bragg-Williams approximation (BWA) and the quasichemical approximation (QCA). The new theoretical framework is obtained by combining (i) the exact analytical expression for the partition function of noninteracting linear k-mers adsorbed in one dimension and its extension to higher dimensions, and (ii) a generalization of BWA and QCA in which the adsorbate can occupy more than one adsorption site. The traditional assumption of a strictly pairwise additive nearest-neighbors interaction is replaced by a more general one, namely that the bond linking a certain atom with any of its neighbors depends considerably on how many of them are actually present (or absent) on the sites in the first coordination shell of the atom. The coverage and temperature dependence of the Helmholtz free energy, chemical potential, configurational entropy, and differential heat of adsorption are given. The formalism (i) reproduces the classical results for monomers, (ii) leads to the exact statistical thermodynamics of nonadditive interacting k-mers adsorbed in one dimension, and (iii) provides a close approximation for two-dimensional systems, taking into account multisite occupancy and nonadditive lateral interactions. Comparisons with Monte Carlo simulations are performed in order to test the validity of the theoretical model. Significant quantitative differences are shown and discussed. In all cases, the QCA appears to be the more accurate approach.Fil: Pinto, Oscar Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Física Aplicada; Argentina. Universidad Nacional de San Luis; ArgentinaFil: Nieto Quintas, Felix Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Física Aplicada; Argentina. Universidad Nacional de San Luis; ArgentinaFil: Ramirez Pastor, Antonio Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Física Aplicada; Argentina. Universidad Nacional de San Luis; ArgentinaAmerican Physical Society2011-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/14151Pinto, Oscar Alejandro; Nieto Quintas, Felix Daniel; Ramirez Pastor, Antonio Jose; Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulations; American Physical Society; Physical Review E: Statistical, Nonlinear And Soft Matter Physics; 84; 6; 12-2011; 61142-611531539-3755enginfo:eu-repo/semantics/altIdentifier/url/http://journals.aps.org/pre/abstract/10.1103/PhysRevE.84.061142info:eu-repo/semantics/altIdentifier/doi/10.1103/PhysRevE.84.061142info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:08:44Zoai:ri.conicet.gov.ar:11336/14151instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 10:08:46.059CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulations
title Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulations
spellingShingle Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulations
Pinto, Oscar Alejandro
Thermodynamics
Nonadditive
Monte Carlo Simulations
title_short Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulations
title_full Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulations
title_fullStr Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulations
title_full_unstemmed Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulations
title_sort Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulations
dc.creator.none.fl_str_mv Pinto, Oscar Alejandro
Nieto Quintas, Felix Daniel
Ramirez Pastor, Antonio Jose
author Pinto, Oscar Alejandro
author_facet Pinto, Oscar Alejandro
Nieto Quintas, Felix Daniel
Ramirez Pastor, Antonio Jose
author_role author
author2 Nieto Quintas, Felix Daniel
Ramirez Pastor, Antonio Jose
author2_role author
author
dc.subject.none.fl_str_mv Thermodynamics
Nonadditive
Monte Carlo Simulations
topic Thermodynamics
Nonadditive
Monte Carlo Simulations
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The statistical thermodynamics of straight rigid rods of length k (k-mers) with nonadditive lateral interactions was developed on a generalization in the spirit of the lattice-gas model and the classical Bragg-Williams approximation (BWA) and the quasichemical approximation (QCA). The new theoretical framework is obtained by combining (i) the exact analytical expression for the partition function of noninteracting linear k-mers adsorbed in one dimension and its extension to higher dimensions, and (ii) a generalization of BWA and QCA in which the adsorbate can occupy more than one adsorption site. The traditional assumption of a strictly pairwise additive nearest-neighbors interaction is replaced by a more general one, namely that the bond linking a certain atom with any of its neighbors depends considerably on how many of them are actually present (or absent) on the sites in the first coordination shell of the atom. The coverage and temperature dependence of the Helmholtz free energy, chemical potential, configurational entropy, and differential heat of adsorption are given. The formalism (i) reproduces the classical results for monomers, (ii) leads to the exact statistical thermodynamics of nonadditive interacting k-mers adsorbed in one dimension, and (iii) provides a close approximation for two-dimensional systems, taking into account multisite occupancy and nonadditive lateral interactions. Comparisons with Monte Carlo simulations are performed in order to test the validity of the theoretical model. Significant quantitative differences are shown and discussed. In all cases, the QCA appears to be the more accurate approach.
Fil: Pinto, Oscar Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Física Aplicada; Argentina. Universidad Nacional de San Luis; Argentina
Fil: Nieto Quintas, Felix Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Física Aplicada; Argentina. Universidad Nacional de San Luis; Argentina
Fil: Ramirez Pastor, Antonio Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico San Luis. Instituto de Física Aplicada; Argentina. Universidad Nacional de San Luis; Argentina
description The statistical thermodynamics of straight rigid rods of length k (k-mers) with nonadditive lateral interactions was developed on a generalization in the spirit of the lattice-gas model and the classical Bragg-Williams approximation (BWA) and the quasichemical approximation (QCA). The new theoretical framework is obtained by combining (i) the exact analytical expression for the partition function of noninteracting linear k-mers adsorbed in one dimension and its extension to higher dimensions, and (ii) a generalization of BWA and QCA in which the adsorbate can occupy more than one adsorption site. The traditional assumption of a strictly pairwise additive nearest-neighbors interaction is replaced by a more general one, namely that the bond linking a certain atom with any of its neighbors depends considerably on how many of them are actually present (or absent) on the sites in the first coordination shell of the atom. The coverage and temperature dependence of the Helmholtz free energy, chemical potential, configurational entropy, and differential heat of adsorption are given. The formalism (i) reproduces the classical results for monomers, (ii) leads to the exact statistical thermodynamics of nonadditive interacting k-mers adsorbed in one dimension, and (iii) provides a close approximation for two-dimensional systems, taking into account multisite occupancy and nonadditive lateral interactions. Comparisons with Monte Carlo simulations are performed in order to test the validity of the theoretical model. Significant quantitative differences are shown and discussed. In all cases, the QCA appears to be the more accurate approach.
publishDate 2011
dc.date.none.fl_str_mv 2011-12
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/14151
Pinto, Oscar Alejandro; Nieto Quintas, Felix Daniel; Ramirez Pastor, Antonio Jose; Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulations; American Physical Society; Physical Review E: Statistical, Nonlinear And Soft Matter Physics; 84; 6; 12-2011; 61142-61153
1539-3755
url http://hdl.handle.net/11336/14151
identifier_str_mv Pinto, Oscar Alejandro; Nieto Quintas, Felix Daniel; Ramirez Pastor, Antonio Jose; Statistical thermodynamics of straight rigid rods with non-additive lateral interactions: Theory and Monte Carlo simulations; American Physical Society; Physical Review E: Statistical, Nonlinear And Soft Matter Physics; 84; 6; 12-2011; 61142-61153
1539-3755
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://journals.aps.org/pre/abstract/10.1103/PhysRevE.84.061142
info:eu-repo/semantics/altIdentifier/doi/10.1103/PhysRevE.84.061142
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Physical Society
publisher.none.fl_str_mv American Physical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.13397

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