On the zeroth-order Hamiltonian for CASPT2 calculations of spin crossover compounds

Complete active space self-consistent field theory (CASSCF) calculations and subsequent second-order perturbation theory treatment (CASPT2) are discussed in the evaluation of the spin-states energy difference (ΔHelec) of a series of seven spin crossover (SCO) compounds. The reference values have bee...

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Detalhes bibliográficos
Autores: Vela Llausí, Sergi, Fumanal Quintana, María, Ribas Ariño, Jordi, Robert, V.
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2016
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/154484
Acesso em linha:https://hdl.handle.net/2445/154484
Access Level:acceso abierto
Palavra-chave:Ferro
Lligands
Iron
Ligands
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repository_id_str
spelling On the zeroth-order Hamiltonian for CASPT2 calculations of spin crossover compoundsVela Llausí, SergiFumanal Quintana, MaríaRibas Ariño, JordiRobert, V.FerroLligandsIronLigandsComplete active space self-consistent field theory (CASSCF) calculations and subsequent second-order perturbation theory treatment (CASPT2) are discussed in the evaluation of the spin-states energy difference (ΔHelec) of a series of seven spin crossover (SCO) compounds. The reference values have been extracted from a combination of experimental measurements and DFT  +  U calculations, as discussed in a recent article (Vela et al., Phys Chem Chem Phys 2015, 17, 16306). It is definitely proven that the critical IPEA parameter used in CASPT2 calculations of ΔHelec, a key parameter in the design of SCO compounds, should be modified with respect to its default value of 0.25 a.u. and increased up to 0.50 a.u. The satisfactory agreement observed previously in the literature might result from an error cancellation originated in the default IPEA, which overestimates the stability of the HS state, and the erroneous atomic orbital basis set contraction of carbon atoms, which stabilizes the LS states.Wiley2020202020162020info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion7 p.application/pdfhttps://hdl.handle.net/2445/154484Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió postprint del document publicat a: https://doi.org/10.1002/jcc.24283Journal of Computational Chemistry, 2016, vol. 37, num. 10, p. 947-953https://doi.org/10.1002/jcc.24283(c) Wiley, 2016info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1544842026-05-29T05:05:01Z
dc.title.none.fl_str_mv On the zeroth-order Hamiltonian for CASPT2 calculations of spin crossover compounds
title On the zeroth-order Hamiltonian for CASPT2 calculations of spin crossover compounds
spellingShingle On the zeroth-order Hamiltonian for CASPT2 calculations of spin crossover compounds
Vela Llausí, Sergi
Ferro
Lligands
Iron
Ligands
title_short On the zeroth-order Hamiltonian for CASPT2 calculations of spin crossover compounds
title_full On the zeroth-order Hamiltonian for CASPT2 calculations of spin crossover compounds
title_fullStr On the zeroth-order Hamiltonian for CASPT2 calculations of spin crossover compounds
title_full_unstemmed On the zeroth-order Hamiltonian for CASPT2 calculations of spin crossover compounds
title_sort On the zeroth-order Hamiltonian for CASPT2 calculations of spin crossover compounds
dc.creator.none.fl_str_mv Vela Llausí, Sergi
Fumanal Quintana, María
Ribas Ariño, Jordi
Robert, V.
author Vela Llausí, Sergi
author_facet Vela Llausí, Sergi
Fumanal Quintana, María
Ribas Ariño, Jordi
Robert, V.
author_role author
author2 Fumanal Quintana, María
Ribas Ariño, Jordi
Robert, V.
author2_role author
author
author
dc.subject.none.fl_str_mv Ferro
Lligands
Iron
Ligands
topic Ferro
Lligands
Iron
Ligands
description Complete active space self-consistent field theory (CASSCF) calculations and subsequent second-order perturbation theory treatment (CASPT2) are discussed in the evaluation of the spin-states energy difference (ΔHelec) of a series of seven spin crossover (SCO) compounds. The reference values have been extracted from a combination of experimental measurements and DFT  +  U calculations, as discussed in a recent article (Vela et al., Phys Chem Chem Phys 2015, 17, 16306). It is definitely proven that the critical IPEA parameter used in CASPT2 calculations of ΔHelec, a key parameter in the design of SCO compounds, should be modified with respect to its default value of 0.25 a.u. and increased up to 0.50 a.u. The satisfactory agreement observed previously in the literature might result from an error cancellation originated in the default IPEA, which overestimates the stability of the HS state, and the erroneous atomic orbital basis set contraction of carbon atoms, which stabilizes the LS states.
publishDate 2016
dc.date.none.fl_str_mv 2016
2020
2020
2020
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/154484
url https://hdl.handle.net/2445/154484
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1002/jcc.24283
Journal of Computational Chemistry, 2016, vol. 37, num. 10, p. 947-953
https://doi.org/10.1002/jcc.24283
dc.rights.none.fl_str_mv (c) Wiley, 2016
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Wiley, 2016
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 7 p.
application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv Articles publicats en revistes (Ciència dels Materials i Química Física)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812455

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