Computational study of Th4+ and Np4+ hydration and hydrolysis of Th4+ from first principles
Autor(a) principal: | |
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Data de Publicação: | 2017 |
Outros Autores: | , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1007/s00894-017-3252-9 http://hdl.handle.net/11449/169461 |
Resumo: | The aqueous solvation of Th and Np in the IV oxidation state was examined using cluster models generated by Monte Carlo simulations and density functional theory embedded within the COSMO continuum model to approximate the effect of bulk water. Our results suggest that the coordination number (CN) for both Th(IV) and NP(IV) should be 9, in accordance to some experimental and theoretical results from the literature. The structural values for average oxygen–metal distances are within 0.01 Å compared to experimental data, and also within the experimental error. The calculated ΔGSol 0 are in very good agreement with experimental reported values, with deviations at CN = 9 lower than 1% for both Th(IV) and Np(IV). The hydrolysis constants are also in very good agreement with experimental values. Finally, our methodology has the advantage of using a GGA functional (BP86) that not only makes the calculations more affordable computationally than hybrid functional or ab initio molecular dynamics simulations (Car-Parrinello) calculations, but also opens the perspective to use resolution of identity (RI) calculations for more extended systems. |
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Repositório Institucional da UNESP |
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Computational study of Th4+ and Np4+ hydration and hydrolysis of Th4+ from first principlesActinides in solutionDFTFree energy of solvation of ionsRelativistic effectsTheoretical hydrolysis constantsThe aqueous solvation of Th and Np in the IV oxidation state was examined using cluster models generated by Monte Carlo simulations and density functional theory embedded within the COSMO continuum model to approximate the effect of bulk water. Our results suggest that the coordination number (CN) for both Th(IV) and NP(IV) should be 9, in accordance to some experimental and theoretical results from the literature. The structural values for average oxygen–metal distances are within 0.01 Å compared to experimental data, and also within the experimental error. The calculated ΔGSol 0 are in very good agreement with experimental reported values, with deviations at CN = 9 lower than 1% for both Th(IV) and Np(IV). The hydrolysis constants are also in very good agreement with experimental values. Finally, our methodology has the advantage of using a GGA functional (BP86) that not only makes the calculations more affordable computationally than hybrid functional or ab initio molecular dynamics simulations (Car-Parrinello) calculations, but also opens the perspective to use resolution of identity (RI) calculations for more extended systems.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Faculdade de Biotecnologia Instituto de Ciências Biológicas Universidade Federal do Pará (UFPA)Departamento de Matemática Universidade Estadual Paulista (UNESP), PO Box 473Instituto de Física Universidade de Brasília (UnB), PO Box 04455Departamento de Matemática Universidade Estadual Paulista (UNESP), PO Box 473CNPq: 157843/2015-7Universidade Federal do Pará (UFPA)Universidade Estadual Paulista (Unesp)Universidade de Brasília (UnB)Amador, Davi H. T.Sambrano, Julio R. [UNESP]Gargano, Ricardode Macedo, Luiz Guilherme M.2018-12-11T16:46:00Z2018-12-11T16:46:00Z2017-03-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://dx.doi.org/10.1007/s00894-017-3252-9Journal of Molecular Modeling, v. 23, n. 3, 2017.0948-50231610-2940http://hdl.handle.net/11449/16946110.1007/s00894-017-3252-92-s2.0-850129647522-s2.0-85012964752.pdfScopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengJournal of Molecular Modeling0,3600,360info:eu-repo/semantics/openAccess2023-10-21T06:08:32Zoai:repositorio.unesp.br:11449/169461Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462023-10-21T06:08:32Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Computational study of Th4+ and Np4+ hydration and hydrolysis of Th4+ from first principles |
title |
Computational study of Th4+ and Np4+ hydration and hydrolysis of Th4+ from first principles |
spellingShingle |
Computational study of Th4+ and Np4+ hydration and hydrolysis of Th4+ from first principles Amador, Davi H. T. Actinides in solution DFT Free energy of solvation of ions Relativistic effects Theoretical hydrolysis constants |
title_short |
Computational study of Th4+ and Np4+ hydration and hydrolysis of Th4+ from first principles |
title_full |
Computational study of Th4+ and Np4+ hydration and hydrolysis of Th4+ from first principles |
title_fullStr |
Computational study of Th4+ and Np4+ hydration and hydrolysis of Th4+ from first principles |
title_full_unstemmed |
Computational study of Th4+ and Np4+ hydration and hydrolysis of Th4+ from first principles |
title_sort |
Computational study of Th4+ and Np4+ hydration and hydrolysis of Th4+ from first principles |
author |
Amador, Davi H. T. |
author_facet |
Amador, Davi H. T. Sambrano, Julio R. [UNESP] Gargano, Ricardo de Macedo, Luiz Guilherme M. |
author_role |
author |
author2 |
Sambrano, Julio R. [UNESP] Gargano, Ricardo de Macedo, Luiz Guilherme M. |
author2_role |
author author author |
dc.contributor.none.fl_str_mv |
Universidade Federal do Pará (UFPA) Universidade Estadual Paulista (Unesp) Universidade de Brasília (UnB) |
dc.contributor.author.fl_str_mv |
Amador, Davi H. T. Sambrano, Julio R. [UNESP] Gargano, Ricardo de Macedo, Luiz Guilherme M. |
dc.subject.por.fl_str_mv |
Actinides in solution DFT Free energy of solvation of ions Relativistic effects Theoretical hydrolysis constants |
topic |
Actinides in solution DFT Free energy of solvation of ions Relativistic effects Theoretical hydrolysis constants |
description |
The aqueous solvation of Th and Np in the IV oxidation state was examined using cluster models generated by Monte Carlo simulations and density functional theory embedded within the COSMO continuum model to approximate the effect of bulk water. Our results suggest that the coordination number (CN) for both Th(IV) and NP(IV) should be 9, in accordance to some experimental and theoretical results from the literature. The structural values for average oxygen–metal distances are within 0.01 Å compared to experimental data, and also within the experimental error. The calculated ΔGSol 0 are in very good agreement with experimental reported values, with deviations at CN = 9 lower than 1% for both Th(IV) and Np(IV). The hydrolysis constants are also in very good agreement with experimental values. Finally, our methodology has the advantage of using a GGA functional (BP86) that not only makes the calculations more affordable computationally than hybrid functional or ab initio molecular dynamics simulations (Car-Parrinello) calculations, but also opens the perspective to use resolution of identity (RI) calculations for more extended systems. |
publishDate |
2017 |
dc.date.none.fl_str_mv |
2017-03-01 2018-12-11T16:46:00Z 2018-12-11T16:46:00Z |
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/10.1007/s00894-017-3252-9 Journal of Molecular Modeling, v. 23, n. 3, 2017. 0948-5023 1610-2940 http://hdl.handle.net/11449/169461 10.1007/s00894-017-3252-9 2-s2.0-85012964752 2-s2.0-85012964752.pdf |
url |
http://dx.doi.org/10.1007/s00894-017-3252-9 http://hdl.handle.net/11449/169461 |
identifier_str_mv |
Journal of Molecular Modeling, v. 23, n. 3, 2017. 0948-5023 1610-2940 10.1007/s00894-017-3252-9 2-s2.0-85012964752 2-s2.0-85012964752.pdf |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Journal of Molecular Modeling 0,360 0,360 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
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 |
|
_version_ |
1803046089190801409 |