期刊
JOURNAL OF CHEMICAL PHYSICS
卷 139, 期 8, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.4818755
关键词
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资金
- Universidad de Buenos Aires [UBACYT 20020100100197, 20020100100502]
- Consejo Nacional de Investigaciones Cientificas y Tecnicas de la Republica Argentina [11220090100061, 11220090100369, 11220080100398]
- Universidad del Pais Vasco [PPM12/05, GIU12/09, UFI11/07]
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. (C) 2013 AIP Publishing LLC.
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