Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry

An expeditious procedure for the challenging computation of the free energy barriers (DGa) for the solvation of carbocations is presented. This procedure is based on Marcus Theory (MT) and the popular B3LYP/6-31G(d)// PCM method, and it allows the easy, accurate and inexpensive prediction of these b...

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Autores: García Martínez, Antonio, Siehl, Hans-Ulrich, Moya Cerero, Santiago de la, Gómez Calzada, Pedro Carlos
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universidad Complutense de Madrid (UCM)
Repositorio:Docta Complutense
Idioma:inglés
OAI Identifier:oai:docta.ucm.es:20.500.14352/105752
Acceso en línea:https://hdl.handle.net/20.500.14352/105752
Access Level:acceso abierto
Palabra clave:547
Computation theory
Energy barriers
Free energy
Carbocations
Química orgánica (Química)
2306 Química Orgánica
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spelling Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistryGarcía Martínez, AntonioSiehl, Hans-UlrichMoya Cerero, Santiago de laGómez Calzada, Pedro Carlos547Computation theoryEnergy barriersFree energyCarbocationsQuímica orgánica (Química)2306 Química OrgánicaAn expeditious procedure for the challenging computation of the free energy barriers (DGa) for the solvation of carbocations is presented. This procedure is based on Marcus Theory (MT) and the popular B3LYP/6-31G(d)// PCM method, and it allows the easy, accurate and inexpensive prediction of these barriers for carbocations of very different stability. This method was validated by the fair mean absolute error (ca. 1.5 kcal mol1 ) achieved in the prediction of 19 known experimental barriers covering a range of ca. 50 kcal mol1 . Interestingly, the new procedure also uses an original method for the calculation of the required inner reorganization energy (Li ) and free energy of reaction (DG). This procedure should pave the way to face computationally the pivotal issue of carbocation chemistry and could be easily extended to any bimolecular organic reaction.Royal Society of ChemistryUniversidad Complutense de Madrid20232023-01-0120232023-01-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/20.500.14352/105752reponame:Docta Complutenseinstname:Universidad Complutense de Madrid (UCM)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2info:eu-repo/semantics/openAccessoai:docta.ucm.es:20.500.14352/1057522026-06-02T12:44:21Z
dc.title.none.fl_str_mv Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry
title Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry
spellingShingle Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry
García Martínez, Antonio
547
Computation theory
Energy barriers
Free energy
Carbocations
Química orgánica (Química)
2306 Química Orgánica
title_short Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry
title_full Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry
title_fullStr Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry
title_full_unstemmed Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry
title_sort Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry
dc.creator.none.fl_str_mv García Martínez, Antonio
Siehl, Hans-Ulrich
Moya Cerero, Santiago de la
Gómez Calzada, Pedro Carlos
author García Martínez, Antonio
author_facet García Martínez, Antonio
Siehl, Hans-Ulrich
Moya Cerero, Santiago de la
Gómez Calzada, Pedro Carlos
author_role author
author2 Siehl, Hans-Ulrich
Moya Cerero, Santiago de la
Gómez Calzada, Pedro Carlos
author2_role author
author
author
dc.contributor.none.fl_str_mv Universidad Complutense de Madrid
dc.subject.none.fl_str_mv 547
Computation theory
Energy barriers
Free energy
Carbocations
Química orgánica (Química)
2306 Química Orgánica
topic 547
Computation theory
Energy barriers
Free energy
Carbocations
Química orgánica (Química)
2306 Química Orgánica
description An expeditious procedure for the challenging computation of the free energy barriers (DGa) for the solvation of carbocations is presented. This procedure is based on Marcus Theory (MT) and the popular B3LYP/6-31G(d)// PCM method, and it allows the easy, accurate and inexpensive prediction of these barriers for carbocations of very different stability. This method was validated by the fair mean absolute error (ca. 1.5 kcal mol1 ) achieved in the prediction of 19 known experimental barriers covering a range of ca. 50 kcal mol1 . Interestingly, the new procedure also uses an original method for the calculation of the required inner reorganization energy (Li ) and free energy of reaction (DG). This procedure should pave the way to face computationally the pivotal issue of carbocation chemistry and could be easily extended to any bimolecular organic reaction.
publishDate 2023
dc.date.none.fl_str_mv 2023
2023-01-01
2023
2023-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/20.500.14352/105752
url https://hdl.handle.net/20.500.14352/105752
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
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
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:Docta Complutense
instname:Universidad Complutense de Madrid (UCM)
instname_str Universidad Complutense de Madrid (UCM)
reponame_str Docta Complutense
collection Docta Complutense
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,81155

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