Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function

Autores
Poelmans, W.; Van Raemdonck, M.; Verstichel, B.; De Baerdemacker, S.; Torre, Alicia; Lain, Luis; Massaccesi, Gustavo Ernesto; Alcoba, Diego Ricardo; Bultinck, B.; Van Neck, D.
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We perform a direct variational determination of the second-order (two-particle) density matrix corresponding to a many-electron system, under a restricted set of the two-index N-representability P-, Q-, and G-conditions. In addition, we impose a set of necessary constraints that the two-particle density matrix must be derivable from a doubly-occupied many-electron wave function, i.e. a singlet wave function for which the Slater determinant decomposition only contains determinants in which spatial orbitals are doubly occupied. We rederive the two-index N-representability conditions first found by Weinhold and Wilson and apply them to various benchmark systems (linear hydrogen chains, He, N2 and CN-). This work is motivated by the fact that a doubly-occupied many-electron wave function captures in many cases the bulk of the static correlation. Compared to the general case, the structure of doubly-occupied two particle density matrices causes the associate semidefinite program to have a very favorable scaling as L3, where L is the number of spatial orbitals. Since the doubly-occupied Hilbert space depends on the choice of the orbitals, variational calculation steps of the two-particle density matrix are interspersed with orbital-optimization steps (based on Jacobi rotations in the space of the spatial orbitals). We also point to the importance of symmetry breaking of the orbitals when performing calculations in a doubly-occupied framework.
Fil: Poelmans, W.. Center For Molecular Modeling; Bélgica
Fil: Van Raemdonck, M.. Department Of Inorganic And Physical Chemistry; Bélgica
Fil: Verstichel, B.. Center For Molecular Modeling; Bélgica
Fil: De Baerdemacker, S.. Department Of Inorganic And Physical Chemistry; Bélgica. Center For Molecular Modeling; Bélgica
Fil: Torre, Alicia. Facultad de Ciencia y Tecnología; España
Fil: Lain, Luis. Facultad de Ciencia y Tecnología; España
Fil: Massaccesi, Gustavo Ernesto. Universidad de Buenos Aires. Ciclo Basico Comun. Departamento de Física, Química y Matemática; Argentina
Fil: Alcoba, Diego Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina
Fil: Bultinck, B.. Department Of Inorganic And Physical Chemistry; Bélgica
Fil: Van Neck, D.. Center For Molecular Modeling; Bélgica
Materia
-
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/48126
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/48126
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave FunctionPoelmans, W.Van Raemdonck, M.Verstichel, B.De Baerdemacker, S.Torre, AliciaLain, LuisMassaccesi, Gustavo ErnestoAlcoba, Diego RicardoBultinck, B.Van Neck, D.-https://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1We perform a direct variational determination of the second-order (two-particle) density matrix corresponding to a many-electron system, under a restricted set of the two-index N-representability P-, Q-, and G-conditions. In addition, we impose a set of necessary constraints that the two-particle density matrix must be derivable from a doubly-occupied many-electron wave function, i.e. a singlet wave function for which the Slater determinant decomposition only contains determinants in which spatial orbitals are doubly occupied. We rederive the two-index N-representability conditions first found by Weinhold and Wilson and apply them to various benchmark systems (linear hydrogen chains, He, N2 and CN-). This work is motivated by the fact that a doubly-occupied many-electron wave function captures in many cases the bulk of the static correlation. Compared to the general case, the structure of doubly-occupied two particle density matrices causes the associate semidefinite program to have a very favorable scaling as L3, where L is the number of spatial orbitals. Since the doubly-occupied Hilbert space depends on the choice of the orbitals, variational calculation steps of the two-particle density matrix are interspersed with orbital-optimization steps (based on Jacobi rotations in the space of the spatial orbitals). We also point to the importance of symmetry breaking of the orbitals when performing calculations in a doubly-occupied framework.Fil: Poelmans, W.. Center For Molecular Modeling; BélgicaFil: Van Raemdonck, M.. Department Of Inorganic And Physical Chemistry; BélgicaFil: Verstichel, B.. Center For Molecular Modeling; BélgicaFil: De Baerdemacker, S.. Department Of Inorganic And Physical Chemistry; Bélgica. Center For Molecular Modeling; BélgicaFil: Torre, Alicia. Facultad de Ciencia y Tecnología; EspañaFil: Lain, Luis. Facultad de Ciencia y Tecnología; EspañaFil: Massaccesi, Gustavo Ernesto. Universidad de Buenos Aires. Ciclo Basico Comun. Departamento de Física, Química y Matemática; ArgentinaFil: Alcoba, Diego Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; ArgentinaFil: Bultinck, B.. Department Of Inorganic And Physical Chemistry; BélgicaFil: Van Neck, D.. Center For Molecular Modeling; BélgicaAmerican Chemical Society2015-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/48126Poelmans, W.; Van Raemdonck, M.; Verstichel, B.; De Baerdemacker, S.; Torre, Alicia; et al.; Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function; American Chemical Society; Journal of Chemical Theory and Computation; 11; 7-2015; 4064-40761549-9618CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jctc.5b00378info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/acs.jctc.5b00378info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-29T12:07:27Zoai:ri.conicet.gov.ar:11336/48126instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-29 12:07:27.437CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function
title Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function
spellingShingle Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function
Poelmans, W.
-
title_short Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function
title_full Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function
title_fullStr Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function
title_full_unstemmed Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function
title_sort Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function
dc.creator.none.fl_str_mv Poelmans, W.
Van Raemdonck, M.
Verstichel, B.
De Baerdemacker, S.
Torre, Alicia
Lain, Luis
Massaccesi, Gustavo Ernesto
Alcoba, Diego Ricardo
Bultinck, B.
Van Neck, D.
author Poelmans, W.
author_facet Poelmans, W.
Van Raemdonck, M.
Verstichel, B.
De Baerdemacker, S.
Torre, Alicia
Lain, Luis
Massaccesi, Gustavo Ernesto
Alcoba, Diego Ricardo
Bultinck, B.
Van Neck, D.
author_role author
author2 Van Raemdonck, M.
Verstichel, B.
De Baerdemacker, S.
Torre, Alicia
Lain, Luis
Massaccesi, Gustavo Ernesto
Alcoba, Diego Ricardo
Bultinck, B.
Van Neck, D.
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv -
topic -
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We perform a direct variational determination of the second-order (two-particle) density matrix corresponding to a many-electron system, under a restricted set of the two-index N-representability P-, Q-, and G-conditions. In addition, we impose a set of necessary constraints that the two-particle density matrix must be derivable from a doubly-occupied many-electron wave function, i.e. a singlet wave function for which the Slater determinant decomposition only contains determinants in which spatial orbitals are doubly occupied. We rederive the two-index N-representability conditions first found by Weinhold and Wilson and apply them to various benchmark systems (linear hydrogen chains, He, N2 and CN-). This work is motivated by the fact that a doubly-occupied many-electron wave function captures in many cases the bulk of the static correlation. Compared to the general case, the structure of doubly-occupied two particle density matrices causes the associate semidefinite program to have a very favorable scaling as L3, where L is the number of spatial orbitals. Since the doubly-occupied Hilbert space depends on the choice of the orbitals, variational calculation steps of the two-particle density matrix are interspersed with orbital-optimization steps (based on Jacobi rotations in the space of the spatial orbitals). We also point to the importance of symmetry breaking of the orbitals when performing calculations in a doubly-occupied framework.
Fil: Poelmans, W.. Center For Molecular Modeling; Bélgica
Fil: Van Raemdonck, M.. Department Of Inorganic And Physical Chemistry; Bélgica
Fil: Verstichel, B.. Center For Molecular Modeling; Bélgica
Fil: De Baerdemacker, S.. Department Of Inorganic And Physical Chemistry; Bélgica. Center For Molecular Modeling; Bélgica
Fil: Torre, Alicia. Facultad de Ciencia y Tecnología; España
Fil: Lain, Luis. Facultad de Ciencia y Tecnología; España
Fil: Massaccesi, Gustavo Ernesto. Universidad de Buenos Aires. Ciclo Basico Comun. Departamento de Física, Química y Matemática; Argentina
Fil: Alcoba, Diego Ricardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina
Fil: Bultinck, B.. Department Of Inorganic And Physical Chemistry; Bélgica
Fil: Van Neck, D.. Center For Molecular Modeling; Bélgica
description We perform a direct variational determination of the second-order (two-particle) density matrix corresponding to a many-electron system, under a restricted set of the two-index N-representability P-, Q-, and G-conditions. In addition, we impose a set of necessary constraints that the two-particle density matrix must be derivable from a doubly-occupied many-electron wave function, i.e. a singlet wave function for which the Slater determinant decomposition only contains determinants in which spatial orbitals are doubly occupied. We rederive the two-index N-representability conditions first found by Weinhold and Wilson and apply them to various benchmark systems (linear hydrogen chains, He, N2 and CN-). This work is motivated by the fact that a doubly-occupied many-electron wave function captures in many cases the bulk of the static correlation. Compared to the general case, the structure of doubly-occupied two particle density matrices causes the associate semidefinite program to have a very favorable scaling as L3, where L is the number of spatial orbitals. Since the doubly-occupied Hilbert space depends on the choice of the orbitals, variational calculation steps of the two-particle density matrix are interspersed with orbital-optimization steps (based on Jacobi rotations in the space of the spatial orbitals). We also point to the importance of symmetry breaking of the orbitals when performing calculations in a doubly-occupied framework.
publishDate 2015
dc.date.none.fl_str_mv 2015-07
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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://hdl.handle.net/11336/48126
Poelmans, W.; Van Raemdonck, M.; Verstichel, B.; De Baerdemacker, S.; Torre, Alicia; et al.; Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function; American Chemical Society; Journal of Chemical Theory and Computation; 11; 7-2015; 4064-4076
1549-9618
CONICET Digital
CONICET
url http://hdl.handle.net/11336/48126
identifier_str_mv Poelmans, W.; Van Raemdonck, M.; Verstichel, B.; De Baerdemacker, S.; Torre, Alicia; et al.; Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function; American Chemical Society; Journal of Chemical Theory and Computation; 11; 7-2015; 4064-4076
1549-9618
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jctc.5b00378
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/acs.jctc.5b00378
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.10058

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