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Abstract:

This work deals with the configuration interaction method when an N-electron Hamiltonian is projected on Slater determinants which are classified according to their seniority number values. We study the spin features of the wave functions and the size of the matrices required to formulate states of any spin symmetry within this treatment. Correlation energies associated with the wave functions arising from the seniority-based configuration interaction procedure are determined for three types of molecular orbital basis: canonical molecular orbitals, natural orbitals, and the orbitals resulting from minimizing the expectation value of the N-electron seniority number operator. The performance of these bases is analyzed by means of numerical results obtained from selected N-electron systems of several spin symmetries. The comparison of the results highlights the efficiency of the molecular orbital basis which minimizes the mean value of the seniority number for a state, yielding energy values closer to those provided by the full configuration interaction procedure. © 2014 AIP Publishing LLC.

Registro:

Documento: Artículo
Título:Configuration interaction wave functions: A seniority number approach
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, Universidad de Buenos Aires, Ciudad Universitaria, 1428 Buenos Aires, Argentina
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
Palabras clave:Molecular orbitals; Configuration interaction method; Configuration interactions; Correlation energy; Expectation values; Full configuration interaction; Natural orbitals; Numerical results; Slater determinants; Wave functions
Año:2014
Volumen:140
Número:23
DOI: http://dx.doi.org/10.1063/1.4882881
Título revista:Journal of Chemical Physics
Título revista abreviado:J Chem Phys
ISSN:00219606
CODEN:JCPSA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219606_v140_n23_p_Alcoba

Referencias:

  • Davidson, E.R., (1972) Rev. Mod. Phys., 44, p. 451. , 10.1103/RevModPhys.44.451
  • Shavitt, I., Rosenberg, B.J., Palakit, S., (1976) Int. J. Quantum Chem., 10, p. 33. , 10.1002/qua.560100804
  • Shavitt, I., (1998) Mol. Phys., 94, p. 3. , 10.1080/00268979809482290
  • Sherrill, C.D., Schaefer III, H.F., (1999) Adv. Quantum Chem., 34, p. 143. , 10.1016/S0065-3276(08)60532-8
  • Bytautas, L., Ivanic, J., Ruedenberg, K., (2003) J. Chem. Phys., 119, p. 8217. , 10.1063/1.1610434
  • Bytautas, L., Ruedenberg, K., (2009) Chem. Phys., 356, p. 64. , 10.1016/j.chemphys.2008.11.021
  • Evangelista, F.A., (2014) J. Chem. Phys., 140, p. 124114. , 10.1063/1.4869192
  • Wasilewski, J., (1989) Int. J. Quantum Chem., 36, p. 503. , 10.1002/qua.560360406
  • Maurice, D., Head-Gordon, M., (1996) J. Phys. Chem., 100, p. 6131. , 10.1021/jp952754j
  • Ring, P., Schuck, P., (1980) The Nuclear Many-Body Problem, , (Springer-Verlag, New York)
  • Koltun, D.S., Eisenberg, J.M., (1988) Quantum Mechanics of Many Degrees of Freedom, , (Wiley, New York)
  • Bytautas, L., Henderson, T.M., Jiménez-Hoyos, C.A., Ellis, J.K., Scuseria, G.E., (2011) J. Chem. Phys., 135, p. 044119. , 10.1063/1.3613706
  • Limacher, P.A., Ayers, P.W., Johnson, P.A., Baerdemacker, S.D., Neck, D.V., Bultinck, P., (2014) Phys. Chem. Chem. Phys., 16, p. 5061. , 10.1039/c3cp53301h
  • Limacher, P.A., Kim, T.D., Ayers, P.W., Johnson, P.A., Baerdemacker, S.D., Neck, D.V., Bultinck, P., (2014) Mol. Phys., 112, p. 853. , 10.1080/00268976.2013.874600
  • Alcoba, D.R., Torre, A., Lain, L., Massaccesi, G.E., Oña, O.B., (2013) J. Chem. Phys., 139, p. 084103. , 10.1063/1.4818755
  • Löwdin, P.O., (1956) Adv. Phys., 5, p. 1. , 10.1080/00018735600101155
  • Giesbertz, K.J.H., (2014) Chem. Phys. Lett., 591, p. 220. , 10.1016/j.cplett.2013.11.038
  • Paldus, J., Jeziorski, B., (1988) Theor. Chim. Acta, 73, p. 81. , 10.1007/BF00528196
  • Alcoba, D.R., Bochicchio, R.C., Lain, L., Torre, A., (2006) Chem. Phys. Lett., 429, p. 286. , 10.1016/j.cplett.2006.07.068
  • Karafiloglou, P., (2009) J. Chem. Phys., 130, p. 164103. , 10.1063/1.3116083
  • Torre, A., Lain, L., (1998) J. Mol. Struct.: THEOCHEM, 426, p. 25. , 10.1016/S0166-1280(97)00304-7
  • Planelles, J., Valdemoro, C., Karwowski, J., (1990) Phys. Rev. A, 41, p. 2391. , 10.1103/PhysRevA.41.2391
  • Valdemoro, C., Torre, A., Lain, L., (1992) Structure, Interactions and Reactivity, , edited by S. Fraga (Elsevier, Amsterdam)
  • Torre, A., Lain, L., Millan, J., (1993) Phys. Rev. A, 47, p. 923. , 10.1103/PhysRevA.47.923
  • Paldus, J., (1974) J. Chem. Phys., 61, p. 5321. , 10.1063/1.1681883
  • Paldus, J., (1976) Theoretical Chemistry: Advances and Perspectives, , edited by H. Eyring and D. Henderson (Academic, New York)
  • Crawford, T.D., Sherrill, C.D., Valeev, E.F., Fermann, J.T., King, R.A., Leininger, M.L., Brown, S.T., Allen, W.D., (2007) J. Comput. Chem., 28, p. 1610. , 10.1002/jcc.20573
  • Subotnik, J.E., Shao, Y., Liang, W., Head-Gordon, M., (2004) J. Chem. Phys., 121, p. 9220. , 10.1063/1.1790971
  • Huzinaga, S., (1965) J. Chem. Phys., 42, p. 1293. , 10.1063/1.1696113
  • Dunning Jr., T.H., (1970) J. Chem. Phys., 53, p. 2823. , 10.1063/1.1674408

Citas:

---------- APA ----------
Alcoba, D.R., Torre, A., Lain, L., Massaccesi, G.E. & Oña, O.B. (2014) . Configuration interaction wave functions: A seniority number approach. Journal of Chemical Physics, 140(23).
http://dx.doi.org/10.1063/1.4882881
---------- CHICAGO ----------
Alcoba, D.R., Torre, A., Lain, L., Massaccesi, G.E., Oña, O.B. "Configuration interaction wave functions: A seniority number approach" . Journal of Chemical Physics 140, no. 23 (2014).
http://dx.doi.org/10.1063/1.4882881
---------- MLA ----------
Alcoba, D.R., Torre, A., Lain, L., Massaccesi, G.E., Oña, O.B. "Configuration interaction wave functions: A seniority number approach" . Journal of Chemical Physics, vol. 140, no. 23, 2014.
http://dx.doi.org/10.1063/1.4882881
---------- VANCOUVER ----------
Alcoba, D.R., Torre, A., Lain, L., Massaccesi, G.E., Oña, O.B. Configuration interaction wave functions: A seniority number approach. J Chem Phys. 2014;140(23).
http://dx.doi.org/10.1063/1.4882881