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Abstract:

The equation obtained by mapping the matrix representation of the Schrödinger equation with the 2nd-order correlation transition matrix elements into the 2-body space is the so called correlation contracted Schrödinger equation (CCSE) (Alcoba, Phys Rev A 2002, 65, 032519). As shown by Alcoba (Phys Rev A 2002, 65, 032519) the solution of the CCSE coincides with that of the Schrödinger equation. Here the attention is focused in the vanishing hypervirial of the correlation operator (GHV), which can be identified with the anti-Hermitian part of the CCSE. A comparative analysis of the GHV and the anti-Hermitian part of the contracted Schrödinger equation (ACSE) indicates that the former is a stronger stationarity condition than the latter. By applying a Heisenberg-like unitary transformation to the G-particle-hole operator (Valdemoro et al., Phys Rev A 2000, 61, 032507), a good approximation of the expectation value of this operator as well as of the GHV is obtained. The method is illustrated for the case of the Beryllium isoelectronic series as well as for the Li2 and BeH2 molecules. The correlation energies obtained are within 98.80-100.09% of the full-configuration interaction ones. The convergence of these calculations was faster when using the GHV than with the ACSE. © 2009 Wiley Periodicals, Inc.

Registro:

Documento: Artículo
Título:The correlation contracted schrodinger equation: An accurate solution of the G-particle-hole hypervirial
Autor:Alcoba, D.R.; Valdemoro, C.; Tel, L.M.; Pérez-Romero, E.
Filiación:Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires 1428, Argentina
Instituto de Matemáticas y Física Fundamental, Consejo Superior de Investigaciones Científicas, Serrano 123, Madrid 28006, Spain
Departamento de Química Física, Facultad de Ciencias Químicas, Universidad de Salamanca, Salamanca 37008, Spain
Palabras clave:Anti-hermitian contracted schrödinger equation; Contracted schrodinger equation; Correlation matrix; Electronic correlation effects; G-matrix; Reduced density matrix; Contracted schrodinger equation; Correlation matrix; Electronic correlation effects; G-matrix; Reduced density matrix; Beryllium; Correlation detectors; Correlation methods; Schrodinger equation; Mathematical operators
Año:2009
Volumen:109
Número:14
Página de inicio:3178
Página de fin:3190
DOI: http://dx.doi.org/10.1002/qua.21943
Título revista:International Journal of Quantum Chemistry
Título revista abreviado:Int J Quantum Chem
ISSN:00207608
CODEN:IJQCB
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00207608_v109_n14_p3178_Alcoba

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Citas:

---------- APA ----------
Alcoba, D.R., Valdemoro, C., Tel, L.M. & Pérez-Romero, E. (2009) . The correlation contracted schrodinger equation: An accurate solution of the G-particle-hole hypervirial. International Journal of Quantum Chemistry, 109(14), 3178-3190.
http://dx.doi.org/10.1002/qua.21943
---------- CHICAGO ----------
Alcoba, D.R., Valdemoro, C., Tel, L.M., Pérez-Romero, E. "The correlation contracted schrodinger equation: An accurate solution of the G-particle-hole hypervirial" . International Journal of Quantum Chemistry 109, no. 14 (2009) : 3178-3190.
http://dx.doi.org/10.1002/qua.21943
---------- MLA ----------
Alcoba, D.R., Valdemoro, C., Tel, L.M., Pérez-Romero, E. "The correlation contracted schrodinger equation: An accurate solution of the G-particle-hole hypervirial" . International Journal of Quantum Chemistry, vol. 109, no. 14, 2009, pp. 3178-3190.
http://dx.doi.org/10.1002/qua.21943
---------- VANCOUVER ----------
Alcoba, D.R., Valdemoro, C., Tel, L.M., Pérez-Romero, E. The correlation contracted schrodinger equation: An accurate solution of the G-particle-hole hypervirial. Int J Quantum Chem. 2009;109(14):3178-3190.
http://dx.doi.org/10.1002/qua.21943