Potentials of mean force in acidic proton transfer reactions in constrained geometries

Free energy barriers associated with the transfer of an excess proton in water and related to the potentials of mean force in proton transfer episodes have been computed in a wide range of thermodynamic states, from low-density amorphous ices to high-temperature liquids under the critical point for...

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Autor: Martí Rabassa, Jordi|||0000-0002-3721-9634
Tipo de recurso: artículo
Fecha de publicación:2016
País:España
Institución:Universitat Politècnica de Catalunya (UPC)
Repositorio:UPCommons. Portal del coneixement obert de la UPC
Idioma:inglés
OAI Identifier:oai:upcommons.upc.edu:2117/97725
Acceso en línea:https://hdl.handle.net/2117/97725
https://dx.doi.org/10.1080/08927022.2016.1239824
Access Level:acceso abierto
Palabra clave:Proton transfer reactions
Molecular dynamics
proton transfer
potential of mean force
constrained water
Protons--Reaccions de transferència
Dinàmica molecular
Àrees temàtiques de la UPC::Física
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spelling Potentials of mean force in acidic proton transfer reactions in constrained geometriesMartí Rabassa, Jordi|||0000-0002-3721-9634Proton transfer reactionsMolecular dynamicsproton transferpotential of mean forceconstrained waterProtons--Reaccions de transferènciaDinàmica molecularÀrees temàtiques de la UPC::FísicaFree energy barriers associated with the transfer of an excess proton in water and related to the potentials of mean force in proton transfer episodes have been computed in a wide range of thermodynamic states, from low-density amorphous ices to high-temperature liquids under the critical point for unconstrained and constrained systems. The latter were represented by set-ups placed inside hydrophobic graphene slabs at the nanometric scale allocating a few water layers, namely one or two in the narrowest case. Water–proton and carbon–proton forces were modelled with a Multi-State Empirical Valence Bond method. As a general trend, a competition between the effects of confinement and temperature is observed on the local hydrogen-bonded structures around the lone proton and, consequently, on the mean force exerted by its environment on the water molecule carrying the proton. Free energy barriers estimated from the computed potentials of mean force tend to rise with the combined effect of increasing temperatures and the packing effect due to a larger extent of hydrophobic confinement. The main reason observed for such enhancement of the free energy barriers was the breaking of the second coordination shell around the lone proton.20162016-10-1720162016-12-02journal articlehttp://purl.org/coar/resource_type/c_6501AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/2117/97725https://dx.doi.org/10.1080/08927022.2016.1239824reponame:UPCommons. Portal del coneixement obert de la UPCinstname:Universitat Politècnica de Catalunya (UPC)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2http://creativecommons.org/licenses/by-nc-nd/3.0/es/info:eu-repo/semantics/openAccessoai:upcommons.upc.edu:2117/977252026-05-27T15:37:01Z
dc.title.none.fl_str_mv Potentials of mean force in acidic proton transfer reactions in constrained geometries
title Potentials of mean force in acidic proton transfer reactions in constrained geometries
spellingShingle Potentials of mean force in acidic proton transfer reactions in constrained geometries
Martí Rabassa, Jordi|||0000-0002-3721-9634
Proton transfer reactions
Molecular dynamics
proton transfer
potential of mean force
constrained water
Protons--Reaccions de transferència
Dinàmica molecular
Àrees temàtiques de la UPC::Física
title_short Potentials of mean force in acidic proton transfer reactions in constrained geometries
title_full Potentials of mean force in acidic proton transfer reactions in constrained geometries
title_fullStr Potentials of mean force in acidic proton transfer reactions in constrained geometries
title_full_unstemmed Potentials of mean force in acidic proton transfer reactions in constrained geometries
title_sort Potentials of mean force in acidic proton transfer reactions in constrained geometries
dc.creator.none.fl_str_mv Martí Rabassa, Jordi|||0000-0002-3721-9634
author Martí Rabassa, Jordi|||0000-0002-3721-9634
author_facet Martí Rabassa, Jordi|||0000-0002-3721-9634
author_role author
dc.subject.none.fl_str_mv Proton transfer reactions
Molecular dynamics
proton transfer
potential of mean force
constrained water
Protons--Reaccions de transferència
Dinàmica molecular
Àrees temàtiques de la UPC::Física
topic Proton transfer reactions
Molecular dynamics
proton transfer
potential of mean force
constrained water
Protons--Reaccions de transferència
Dinàmica molecular
Àrees temàtiques de la UPC::Física
description Free energy barriers associated with the transfer of an excess proton in water and related to the potentials of mean force in proton transfer episodes have been computed in a wide range of thermodynamic states, from low-density amorphous ices to high-temperature liquids under the critical point for unconstrained and constrained systems. The latter were represented by set-ups placed inside hydrophobic graphene slabs at the nanometric scale allocating a few water layers, namely one or two in the narrowest case. Water–proton and carbon–proton forces were modelled with a Multi-State Empirical Valence Bond method. As a general trend, a competition between the effects of confinement and temperature is observed on the local hydrogen-bonded structures around the lone proton and, consequently, on the mean force exerted by its environment on the water molecule carrying the proton. Free energy barriers estimated from the computed potentials of mean force tend to rise with the combined effect of increasing temperatures and the packing effect due to a larger extent of hydrophobic confinement. The main reason observed for such enhancement of the free energy barriers was the breaking of the second coordination shell around the lone proton.
publishDate 2016
dc.date.none.fl_str_mv 2016
2016-10-17
2016
2016-12-02
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
AM
http://purl.org/coar/version/c_ab4af688f83e57aa
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/2117/97725
https://dx.doi.org/10.1080/08927022.2016.1239824
url https://hdl.handle.net/2117/97725
https://dx.doi.org/10.1080/08927022.2016.1239824
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2

http://creativecommons.org/licenses/by-nc-nd/3.0/es/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2

http://creativecommons.org/licenses/by-nc-nd/3.0/es/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:UPCommons. Portal del coneixement obert de la UPC
instname:Universitat Politècnica de Catalunya (UPC)
instname_str Universitat Politècnica de Catalunya (UPC)
reponame_str UPCommons. Portal del coneixement obert de la UPC
collection UPCommons. Portal del coneixement obert de la UPC
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