This work proposes the variational determination of two-electron reduced density matrices corresponding to the ground state of N-electron systems within the doubly occupied-configuration-interaction methodology. The P, Q, and G two-index N-representability conditions have been extended to the T1 and T2 (T2′) three-index ones and the resulting optimization problem has been addressed using a standard semidefinite program. We report results obtained from the doubly occupied-configuration-interaction method, from the two-index constraint variational procedure and from the two- and three-index constraint variational treatment. The discussion of these results along with a study of the computational cost demanded shows the usefulness of our proposal.
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14 January 2018
Research Article|
January 09 2018
Direct variational determination of the two-electron reduced density matrix for doubly occupied-configuration-interaction wave functions: The influence of three-index N-representability conditions
Diego R. Alcoba;
Diego R. Alcoba
1
Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria
, 1428 Buenos Aires, Argentina
2
Instituto de Física de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, Ciudad Universitaria
, 1428 Buenos Aires, Argentina
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Alicia Torre
;
Alicia Torre
3
Departamento de Química Física, Facultad de Ciencia y Tecnología
, Universidad del País Vasco. Apdo. 644, E-48080 Bilbao, Spain
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Luis Lain
;
Luis Lain
3
Departamento de Química Física, Facultad de Ciencia y Tecnología
, Universidad del País Vasco. Apdo. 644, E-48080 Bilbao, Spain
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Gustavo E. Massaccesi;
Gustavo E. Massaccesi
4
Departamento de Ciencias Exactas, Ciclo Básico Común, Universidad de Buenos Aires, Ciudad Universitaria
, 1428 Buenos Aires, Argentina
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Ofelia B. Oña;
Ofelia B. Oña
5
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas, Universidad Nacional de La Plata, CCT La Plata, Consejo Nacional de Investigaciones Científicas y Técnicas. Diag. 113 y 64 (S/N)
, Sucursal 4, CC 16, 1900 La Plata, Argentina
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Eduardo M. Honoré;
Eduardo M. Honoré
1
Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria
, 1428 Buenos Aires, Argentina
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Ward Poelmans
;
Ward Poelmans
6
Center for Molecular Modeling, Ghent University
, Technologiepark 903, B-9052 Zwijnaarde, Belgium
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Dimitri Van Neck;
Dimitri Van Neck
6
Center for Molecular Modeling, Ghent University
, Technologiepark 903, B-9052 Zwijnaarde, Belgium
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Patrick Bultinck
;
Patrick Bultinck
a)
7
Department of Inorganic and Physical Chemistry, Ghent University
, Krijgslaan 281 (S3), 9000 Gent, Belgium
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Stijn De Baerdemacker
Stijn De Baerdemacker
6
Center for Molecular Modeling, Ghent University
, Technologiepark 903, B-9052 Zwijnaarde, Belgium
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a)
Electronic mail: Patrick.Bultinck@UGent.be
J. Chem. Phys. 148, 024105 (2018)
Article history
Received:
October 10 2017
Accepted:
December 19 2017
Citation
Diego R. Alcoba, Alicia Torre, Luis Lain, Gustavo E. Massaccesi, Ofelia B. Oña, Eduardo M. Honoré, Ward Poelmans, Dimitri Van Neck, Patrick Bultinck, Stijn De Baerdemacker; Direct variational determination of the two-electron reduced density matrix for doubly occupied-configuration-interaction wave functions: The influence of three-index N-representability conditions. J. Chem. Phys. 14 January 2018; 148 (2): 024105. https://doi.org/10.1063/1.5008811
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