Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions

Autores
Alcoba, Diego Ricardo; Torre, Alicia; Lain, Luis; Massaccesi, Gustavo Ernesto; Oña, Ofelia Beatriz
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
This work extends the concept of seniority number, which has been widely used for classifying N-electron Slater determinants, to wave functions of N electrons and spin S, as well as to N-electron spin-adapted Hilbert spaces. We propose a spin-free formulation of the seniority number operator and perform a study on the behavior of the expectation values of this operator under transformations of the molecular basis sets. This study leads to propose a quantitative evaluation for the convergence of the expansions of the wave functions in terms of Slater determinants. The non-invariant character of the seniority number operator expectation value of a wave function with respect to a unitary transformation of the molecular orbital basis set, allows us to search for a change of basis which minimizes that expectation value. The results found in the description of wave functions of selected atoms and molecules show that the expansions expressed in these bases exhibit a more rapid convergence than those formulated in the canonical molecular orbital bases and even in the natural orbital ones.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
Materia
Química
Física
Seniority number
Configuration interaction
Compactness wave function
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/104325

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repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Seniority number in spin-adapted spaces and compactness of configuration interaction wave functionsAlcoba, Diego RicardoTorre, AliciaLain, LuisMassaccesi, Gustavo ErnestoOña, Ofelia BeatrizQuímicaFísicaSeniority numberConfiguration interactionCompactness wave functionThis work extends the concept of seniority number, which has been widely used for classifying N-electron Slater determinants, to wave functions of N electrons and spin S, as well as to N-electron spin-adapted Hilbert spaces. We propose a spin-free formulation of the seniority number operator and perform a study on the behavior of the expectation values of this operator under transformations of the molecular basis sets. This study leads to propose a quantitative evaluation for the convergence of the expansions of the wave functions in terms of Slater determinants. The non-invariant character of the seniority number operator expectation value of a wave function with respect to a unitary transformation of the molecular orbital basis set, allows us to search for a change of basis which minimizes that expectation value. The results found in the description of wave functions of selected atoms and molecules show that the expansions expressed in these bases exhibit a more rapid convergence than those formulated in the canonical molecular orbital bases and even in the natural orbital ones.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas2013-08-23info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf84103-85103http://sedici.unlp.edu.ar/handle/10915/104325enginfo:eu-repo/semantics/altIdentifier/url/http://hdl.handle.net/11336/2449info:eu-repo/semantics/altIdentifier/issn/0021-9606info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4818755info:eu-repo/semantics/altIdentifier/hdl/11336/2449info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/2.5/ar/Creative Commons Attribution-NonCommercial-ShareAlike 2.5 Argentina (CC BY-NC-SA 2.5)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:22:42Zoai:sedici.unlp.edu.ar:10915/104325Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:22:43.137SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions
title Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions
spellingShingle Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions
Alcoba, Diego Ricardo
Química
Física
Seniority number
Configuration interaction
Compactness wave function
title_short Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions
title_full Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions
title_fullStr Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions
title_full_unstemmed Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions
title_sort Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions
dc.creator.none.fl_str_mv Alcoba, Diego Ricardo
Torre, Alicia
Lain, Luis
Massaccesi, Gustavo Ernesto
Oña, Ofelia Beatriz
author Alcoba, Diego Ricardo
author_facet Alcoba, Diego Ricardo
Torre, Alicia
Lain, Luis
Massaccesi, Gustavo Ernesto
Oña, Ofelia Beatriz
author_role author
author2 Torre, Alicia
Lain, Luis
Massaccesi, Gustavo Ernesto
Oña, Ofelia Beatriz
author2_role author
author
author
author
dc.subject.none.fl_str_mv Química
Física
Seniority number
Configuration interaction
Compactness wave function
topic Química
Física
Seniority number
Configuration interaction
Compactness wave function
dc.description.none.fl_txt_mv This work extends the concept of seniority number, which has been widely used for classifying N-electron Slater determinants, to wave functions of N electrons and spin S, as well as to N-electron spin-adapted Hilbert spaces. We propose a spin-free formulation of the seniority number operator and perform a study on the behavior of the expectation values of this operator under transformations of the molecular basis sets. This study leads to propose a quantitative evaluation for the convergence of the expansions of the wave functions in terms of Slater determinants. The non-invariant character of the seniority number operator expectation value of a wave function with respect to a unitary transformation of the molecular orbital basis set, allows us to search for a change of basis which minimizes that expectation value. The results found in the description of wave functions of selected atoms and molecules show that the expansions expressed in these bases exhibit a more rapid convergence than those formulated in the canonical molecular orbital bases and even in the natural orbital ones.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
description This work extends the concept of seniority number, which has been widely used for classifying N-electron Slater determinants, to wave functions of N electrons and spin S, as well as to N-electron spin-adapted Hilbert spaces. We propose a spin-free formulation of the seniority number operator and perform a study on the behavior of the expectation values of this operator under transformations of the molecular basis sets. This study leads to propose a quantitative evaluation for the convergence of the expansions of the wave functions in terms of Slater determinants. The non-invariant character of the seniority number operator expectation value of a wave function with respect to a unitary transformation of the molecular orbital basis set, allows us to search for a change of basis which minimizes that expectation value. The results found in the description of wave functions of selected atoms and molecules show that the expansions expressed in these bases exhibit a more rapid convergence than those formulated in the canonical molecular orbital bases and even in the natural orbital ones.
publishDate 2013
dc.date.none.fl_str_mv 2013-08-23
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
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://sedici.unlp.edu.ar/handle/10915/104325
url http://sedici.unlp.edu.ar/handle/10915/104325
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://hdl.handle.net/11336/2449
info:eu-repo/semantics/altIdentifier/issn/0021-9606
info:eu-repo/semantics/altIdentifier/doi/10.1063/1.4818755
info:eu-repo/semantics/altIdentifier/hdl/11336/2449
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Creative Commons Attribution-NonCommercial-ShareAlike 2.5 Argentina (CC BY-NC-SA 2.5)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Creative Commons Attribution-NonCommercial-ShareAlike 2.5 Argentina (CC BY-NC-SA 2.5)
dc.format.none.fl_str_mv application/pdf
84103-85103
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
instname:Universidad Nacional de La Plata
instacron:UNLP
reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
instname_str Universidad Nacional de La Plata
instacron_str UNLP
institution UNLP
repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
repository.mail.fl_str_mv alira@sedici.unlp.edu.ar
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