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Abstract:

In this work we project the Hamiltonian of an N-electron system onto a set of N-electron determinants cataloged by their seniority numbers and their excitation levels with respect to a reference determinant. We show that, in open-shell systems, the diagonalization of the N-electron Hamiltonian matrix leads to eigenstates of the operator Ŝ2 when the excitation levels are counted in terms of spatial orbitals instead of spin-orbitals. Our proposal is based on the commutation relations between the N-electron operators seniority number and spatial excitation level, as well as between these operators and the spin operators Ŝ2 and Ŝz. Energy and 〈Ŝ2〉 expectation values of molecular systems obtained from our procedure are compared with those arising from the standard hybrid configuration interaction methods based on seniority numbers and spin-orbital-excitation levels. We analyze the behavior of these methods, evaluating their computational costs and establishing their usefulness. © 2018 Elsevier Inc.

Registro:

Documento: Artículo
Título:Hybrid Treatments Based on Determinant Seniority Numbers and Spatial Excitation Levels in the Configuration Interaction Framework
Autor:Alcoba, D.R.; Torre, A.; Lain, L.; Oña, O.B.; Massaccesi, G.E.; Capuzzi, P.
Filiación:Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires, Argentina
Instituto de Física de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, Buenos Aires, Argentina
Facultad de Ciencia y Tecnología, Universidad del País Vasco, Bilbao, Spain
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas, Universidad Nacional de La Plata, CCT La Plata, Consejo Nacional de Investigaciones Científicas y Técnicas, La Plata, Argentina
Ciclo Básico Común, Universidad de Buenos Aires, Buenos Aires, Argentina
Palabras clave:Configuration interaction methodology; Excitation level operators; Excitation levels in N-electron determinants; Hybrid methods in CI treatments; Seniority number of N-electron determinants; Seniority number operators; Spin contamination of wave functions
Año:2018
Volumen:76
Página de inicio:315
Página de fin:332
DOI: http://dx.doi.org/10.1016/bs.aiq.2017.05.003
Título revista:Advances in Quantum Chemistry
Título revista abreviado:Adv. Quantum Chem.
ISSN:00653276
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00653276_v76_n_p315_Alcoba

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Citas:

---------- APA ----------
Alcoba, D.R., Torre, A., Lain, L., Oña, O.B., Massaccesi, G.E. & Capuzzi, P. (2018) . Hybrid Treatments Based on Determinant Seniority Numbers and Spatial Excitation Levels in the Configuration Interaction Framework. Advances in Quantum Chemistry, 76, 315-332.
http://dx.doi.org/10.1016/bs.aiq.2017.05.003
---------- CHICAGO ----------
Alcoba, D.R., Torre, A., Lain, L., Oña, O.B., Massaccesi, G.E., Capuzzi, P. "Hybrid Treatments Based on Determinant Seniority Numbers and Spatial Excitation Levels in the Configuration Interaction Framework" . Advances in Quantum Chemistry 76 (2018) : 315-332.
http://dx.doi.org/10.1016/bs.aiq.2017.05.003
---------- MLA ----------
Alcoba, D.R., Torre, A., Lain, L., Oña, O.B., Massaccesi, G.E., Capuzzi, P. "Hybrid Treatments Based on Determinant Seniority Numbers and Spatial Excitation Levels in the Configuration Interaction Framework" . Advances in Quantum Chemistry, vol. 76, 2018, pp. 315-332.
http://dx.doi.org/10.1016/bs.aiq.2017.05.003
---------- VANCOUVER ----------
Alcoba, D.R., Torre, A., Lain, L., Oña, O.B., Massaccesi, G.E., Capuzzi, P. Hybrid Treatments Based on Determinant Seniority Numbers and Spatial Excitation Levels in the Configuration Interaction Framework. Adv. Quantum Chem. 2018;76:315-332.
http://dx.doi.org/10.1016/bs.aiq.2017.05.003