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Abstract:

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. © 2013 AIP Publishing LLC.

Registro:

Documento: Artículo
Título:Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions
Autor:Alcoba, D.R.; Torre, A.; Lain, L.; Massaccesi, G.E.; Oña, O.B.
Filiación:Departamento de Física, Facultad de Ciencias Exactas y Naturales, Ciudad Universitaria, 1428 Buenos Aires, Argentina
Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad Del País Vasco, Apdo. 644, E-48080 Bilbao, Spain
Departamento de Ciencias Exactas, Ciclo Básico Común, Ciudad Universitaria, 1428 Buenos Aires, Argentina
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas, Universidad Nacional de la Plata, Consejo Nacional de Investigaciones Cientízficas y Técnicas, Diag. 113 y 64 (S/N), Sucursal 4, CC 16, x1900 La Plata, Argentina
Palabras clave:Change of basis; Configuration interactions; Expectation values; Natural orbitals; Quantitative evaluation; Rapid convergence; Slater determinants; Unitary transformations; Electrospinning; Magnetic moments; Molecular orbitals; Wave functions
Año:2013
Volumen:139
Número:8
DOI: http://dx.doi.org/10.1063/1.4818755
Título revista:Journal of Chemical Physics
Título revista abreviado:J Chem Phys
ISSN:00219606
CODEN:JCPSA
PDF:https://bibliotecadigital.exactas.uba.ar/download/paper/paper_00219606_v139_n8_p_Alcoba.pdf
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219606_v139_n8_p_Alcoba

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Citas:

---------- APA ----------
Alcoba, D.R., Torre, A., Lain, L., Massaccesi, G.E. & Oña, O.B. (2013) . Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions. Journal of Chemical Physics, 139(8).
http://dx.doi.org/10.1063/1.4818755
---------- CHICAGO ----------
Alcoba, D.R., Torre, A., Lain, L., Massaccesi, G.E., Oña, O.B. "Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions" . Journal of Chemical Physics 139, no. 8 (2013).
http://dx.doi.org/10.1063/1.4818755
---------- MLA ----------
Alcoba, D.R., Torre, A., Lain, L., Massaccesi, G.E., Oña, O.B. "Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions" . Journal of Chemical Physics, vol. 139, no. 8, 2013.
http://dx.doi.org/10.1063/1.4818755
---------- VANCOUVER ----------
Alcoba, D.R., Torre, A., Lain, L., Massaccesi, G.E., Oña, O.B. Seniority number in spin-adapted spaces and compactness of configuration interaction wave functions. J Chem Phys. 2013;139(8).
http://dx.doi.org/10.1063/1.4818755