Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures

Autores
Videla, Pablo Ernesto; Rossky, Peter J.; Laria, Daniel Hector
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We use ring-polymer-molecular-dynamics (RPMD) techniques and the semi-empirical q-TIP4P/F water model to investigate the relationship between hydrogen bond connectivity and the charac- teristics of nuclear position fluctuations, including explicit incorporation of quantum effects, for the energetically low lying isomers of the prototype cluster [H2O]8 at T = 50 K and at 150 K. Our results reveal that tunneling and zero-point energy effects lead to sensible increments in the magnitudes of the fluctuations of intra and intermolecular distances. The degree of proton spatial delocalization is found to map logically with the hydrogen-bond connectivity pattern of the cluster. Dangling hydro- gen bonds exhibit the largest extent of spatial delocalization and participate in shorter intramolecular O-H bonds. Combined effects from quantum and polarization fluctuations on the resulting individ- ual dipole moments are also examined. From the dynamical side, we analyze the characteristics of the infrared absorption spectrum. The incorporation of nuclear quantum fluctuations promotes red shifts and sensible broadening relative to the classical profile, bringing the simulation results in much more satisfactory agreement with direct experimental information in the mid and high fre- quency range of the stretching band. While RPMD predictions overestimate the peak position of the low frequency shoulder, the overall agreement with that reported using an accurate, parame- terized, many-body potential is reasonable, and far superior to that one obtains by implementing a partially adiabatic centroid molecular dynamics approach. Quantum effects on the collective dynam- ics, as reported by instantaneous normal modes, are also discussed
Fil: Videla, Pablo Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; Argentina
Fil: Rossky, Peter J.. University of Texas at Austin; Estados Unidos
Fil: Laria, Daniel Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Comision Nacional de Energia Atomica. Gerencia Quimica. CAC; Argentina
Materia
PATH INTEGRALS
NANOAGREGADOS ACUOSOS
FLUCTUACIONES NUCLEARES
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:11336/7973

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spelling Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperaturesVidela, Pablo ErnestoRossky, Peter J.Laria, Daniel HectorPATH INTEGRALSNANOAGREGADOS ACUOSOSFLUCTUACIONES NUCLEAREShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We use ring-polymer-molecular-dynamics (RPMD) techniques and the semi-empirical q-TIP4P/F water model to investigate the relationship between hydrogen bond connectivity and the charac- teristics of nuclear position fluctuations, including explicit incorporation of quantum effects, for the energetically low lying isomers of the prototype cluster [H2O]8 at T = 50 K and at 150 K. Our results reveal that tunneling and zero-point energy effects lead to sensible increments in the magnitudes of the fluctuations of intra and intermolecular distances. The degree of proton spatial delocalization is found to map logically with the hydrogen-bond connectivity pattern of the cluster. Dangling hydro- gen bonds exhibit the largest extent of spatial delocalization and participate in shorter intramolecular O-H bonds. Combined effects from quantum and polarization fluctuations on the resulting individ- ual dipole moments are also examined. From the dynamical side, we analyze the characteristics of the infrared absorption spectrum. The incorporation of nuclear quantum fluctuations promotes red shifts and sensible broadening relative to the classical profile, bringing the simulation results in much more satisfactory agreement with direct experimental information in the mid and high fre- quency range of the stretching band. While RPMD predictions overestimate the peak position of the low frequency shoulder, the overall agreement with that reported using an accurate, parame- terized, many-body potential is reasonable, and far superior to that one obtains by implementing a partially adiabatic centroid molecular dynamics approach. Quantum effects on the collective dynam- ics, as reported by instantaneous normal modes, are also discussedFil: Videla, Pablo Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; ArgentinaFil: Rossky, Peter J.. University of Texas at Austin; Estados UnidosFil: Laria, Daniel Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Comision Nacional de Energia Atomica. Gerencia Quimica. CAC; ArgentinaAmerican Institute Of Physics2013-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/7973Videla, Pablo Ernesto; Rossky, Peter J.; Laria, Daniel Hector; Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures; American Institute Of Physics; Journal Of Chemical Physics; 139; 10-2013; 134715-1347150021-9606enginfo:eu-repo/semantics/altIdentifier/doi/10.1063/1.4827935info:eu-repo/semantics/altIdentifier/url/http://scitation.aip.org/content/aip/journal/jcp/139/17/10.1063/1.4827935info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:38:25Zoai:ri.conicet.gov.ar:11336/7973instacron: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:34982025-09-29 10:38:25.37CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures
title Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures
spellingShingle Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures
Videla, Pablo Ernesto
PATH INTEGRALS
NANOAGREGADOS ACUOSOS
FLUCTUACIONES NUCLEARES
title_short Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures
title_full Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures
title_fullStr Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures
title_full_unstemmed Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures
title_sort Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures
dc.creator.none.fl_str_mv Videla, Pablo Ernesto
Rossky, Peter J.
Laria, Daniel Hector
author Videla, Pablo Ernesto
author_facet Videla, Pablo Ernesto
Rossky, Peter J.
Laria, Daniel Hector
author_role author
author2 Rossky, Peter J.
Laria, Daniel Hector
author2_role author
author
dc.subject.none.fl_str_mv PATH INTEGRALS
NANOAGREGADOS ACUOSOS
FLUCTUACIONES NUCLEARES
topic PATH INTEGRALS
NANOAGREGADOS ACUOSOS
FLUCTUACIONES NUCLEARES
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We use ring-polymer-molecular-dynamics (RPMD) techniques and the semi-empirical q-TIP4P/F water model to investigate the relationship between hydrogen bond connectivity and the charac- teristics of nuclear position fluctuations, including explicit incorporation of quantum effects, for the energetically low lying isomers of the prototype cluster [H2O]8 at T = 50 K and at 150 K. Our results reveal that tunneling and zero-point energy effects lead to sensible increments in the magnitudes of the fluctuations of intra and intermolecular distances. The degree of proton spatial delocalization is found to map logically with the hydrogen-bond connectivity pattern of the cluster. Dangling hydro- gen bonds exhibit the largest extent of spatial delocalization and participate in shorter intramolecular O-H bonds. Combined effects from quantum and polarization fluctuations on the resulting individ- ual dipole moments are also examined. From the dynamical side, we analyze the characteristics of the infrared absorption spectrum. The incorporation of nuclear quantum fluctuations promotes red shifts and sensible broadening relative to the classical profile, bringing the simulation results in much more satisfactory agreement with direct experimental information in the mid and high fre- quency range of the stretching band. While RPMD predictions overestimate the peak position of the low frequency shoulder, the overall agreement with that reported using an accurate, parame- terized, many-body potential is reasonable, and far superior to that one obtains by implementing a partially adiabatic centroid molecular dynamics approach. Quantum effects on the collective dynam- ics, as reported by instantaneous normal modes, are also discussed
Fil: Videla, Pablo Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; Argentina
Fil: Rossky, Peter J.. University of Texas at Austin; Estados Unidos
Fil: Laria, Daniel Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Comision Nacional de Energia Atomica. Gerencia Quimica. CAC; Argentina
description We use ring-polymer-molecular-dynamics (RPMD) techniques and the semi-empirical q-TIP4P/F water model to investigate the relationship between hydrogen bond connectivity and the charac- teristics of nuclear position fluctuations, including explicit incorporation of quantum effects, for the energetically low lying isomers of the prototype cluster [H2O]8 at T = 50 K and at 150 K. Our results reveal that tunneling and zero-point energy effects lead to sensible increments in the magnitudes of the fluctuations of intra and intermolecular distances. The degree of proton spatial delocalization is found to map logically with the hydrogen-bond connectivity pattern of the cluster. Dangling hydro- gen bonds exhibit the largest extent of spatial delocalization and participate in shorter intramolecular O-H bonds. Combined effects from quantum and polarization fluctuations on the resulting individ- ual dipole moments are also examined. From the dynamical side, we analyze the characteristics of the infrared absorption spectrum. The incorporation of nuclear quantum fluctuations promotes red shifts and sensible broadening relative to the classical profile, bringing the simulation results in much more satisfactory agreement with direct experimental information in the mid and high fre- quency range of the stretching band. While RPMD predictions overestimate the peak position of the low frequency shoulder, the overall agreement with that reported using an accurate, parame- terized, many-body potential is reasonable, and far superior to that one obtains by implementing a partially adiabatic centroid molecular dynamics approach. Quantum effects on the collective dynam- ics, as reported by instantaneous normal modes, are also discussed
publishDate 2013
dc.date.none.fl_str_mv 2013-10
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/11336/7973
Videla, Pablo Ernesto; Rossky, Peter J.; Laria, Daniel Hector; Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures; American Institute Of Physics; Journal Of Chemical Physics; 139; 10-2013; 134715-134715
0021-9606
url http://hdl.handle.net/11336/7973
identifier_str_mv Videla, Pablo Ernesto; Rossky, Peter J.; Laria, Daniel Hector; Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures; American Institute Of Physics; Journal Of Chemical Physics; 139; 10-2013; 134715-134715
0021-9606
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4827935
info:eu-repo/semantics/altIdentifier/url/http://scitation.aip.org/content/aip/journal/jcp/139/17/10.1063/1.4827935
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
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 reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
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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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