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Poelmans, W.; Van Raemdonck, M.; Verstichel, B.; De Baerdemacker, S.; Torre, A.; Lain, L.; Massaccesi, G.E.; Alcoba, D.R.; Bultinck, P.; Van Neck, D. "Variational Optimization of the Second-Order Density Matrix Corresponding to a Seniority-Zero Configuration Interaction Wave Function" (2015) Journal of Chemical Theory and Computation. 11(9):4064-4076
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Abstract:

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. © 2015 American Chemical Society.

Registro:

Documento: Artículo
Título:Variational Optimization of the Second-Order Density Matrix Corresponding to a Seniority-Zero Configuration Interaction Wave Function
Autor:Poelmans, W.; Van Raemdonck, M.; Verstichel, B.; De Baerdemacker, S.; Torre, A.; Lain, L.; Massaccesi, G.E.; Alcoba, D.R.; Bultinck, P.; Van Neck, D.
Filiación:Center for Molecular Modeling, Ghent University, Technologiepark 903, Zwijnaarde, 9052, Belgium
Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281 (S3), Gent, 9000, Belgium
Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad Del País Vasco, Apdo. 644, Bilbao, E-48080, Spain
Departamento de Ciencias Exactas, Ciclo Básico Común, Universidad de Buenos Aires, Ciudad Universitaria, Buenos Aires, 1428, Argentina
Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Instituto de Física de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, Ciudad Universitaria, Buenos Aires, 1428, Argentina
Año:2015
Volumen:11
Número:9
Página de inicio:4064
Página de fin:4076
DOI: http://dx.doi.org/10.1021/acs.jctc.5b00378
Título revista:Journal of Chemical Theory and Computation
Título revista abreviado:J. Chem. Theory Comput.
ISSN:15499618
CODEN:JCTCC
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15499618_v11_n9_p4064_Poelmans

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Citas:

---------- APA ----------
Poelmans, W., Van Raemdonck, M., Verstichel, B., De Baerdemacker, S., Torre, A., Lain, L., Massaccesi, G.E.,..., Van Neck, D. (2015) . Variational Optimization of the Second-Order Density Matrix Corresponding to a Seniority-Zero Configuration Interaction Wave Function. Journal of Chemical Theory and Computation, 11(9), 4064-4076.
http://dx.doi.org/10.1021/acs.jctc.5b00378
---------- CHICAGO ----------
Poelmans, W., Van Raemdonck, M., Verstichel, B., De Baerdemacker, S., Torre, A., Lain, L., et al. "Variational Optimization of the Second-Order Density Matrix Corresponding to a Seniority-Zero Configuration Interaction Wave Function" . Journal of Chemical Theory and Computation 11, no. 9 (2015) : 4064-4076.
http://dx.doi.org/10.1021/acs.jctc.5b00378
---------- MLA ----------
Poelmans, W., Van Raemdonck, M., Verstichel, B., De Baerdemacker, S., Torre, A., Lain, L., et al. "Variational Optimization of the Second-Order Density Matrix Corresponding to a Seniority-Zero Configuration Interaction Wave Function" . Journal of Chemical Theory and Computation, vol. 11, no. 9, 2015, pp. 4064-4076.
http://dx.doi.org/10.1021/acs.jctc.5b00378
---------- VANCOUVER ----------
Poelmans, W., Van Raemdonck, M., Verstichel, B., De Baerdemacker, S., Torre, A., Lain, L., et al. Variational Optimization of the Second-Order Density Matrix Corresponding to a Seniority-Zero Configuration Interaction Wave Function. J. Chem. Theory Comput. 2015;11(9):4064-4076.
http://dx.doi.org/10.1021/acs.jctc.5b00378