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Theoretical Chemistry Accounts

, Volume 98, Issue 4, pp 182–191 | Cite as

Superposition of nonorthogonal Slater determinants towards electron correlation problems

  • Seiichiro Ten-no
Regular Article

Abstract.

We propose variational and nonvariational methods based on the superposition of nonorthogonal Slater determinants. Properties of the reference functions are discussed. In the nonorthogonal configuration interaction method, all the excited configurations of multiple determinants are integrated into a variational space. An efficient way to manipulate matrix elements over determinants of distinct vacuums is presented by introducing similarity transformed operator and bracket transformations. The method enables us to map a matrix multiplication in the nonorthogonal problem to an orthogonal one, and thus maintains a fundamental scaling property along with the amount of data processed in the corresponding orthogonal configuration interaction method. Furthermore, we discuss a coupled-cluster theory employing a vacuum-dependent wave operator, which is entirely size consistent as well as core extensive. These methods are applied to H2O + nHe(n = 0−2) and a single-bond dissociation of the HF molecule, compared with conventional methods including full and multireference configuration interaction methods.

Key words: Nonorthogonal Slater determinants Orbital relaxation Similarity transformation Bracket transformation Coupled-cluster theory 

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Copyright information

© Springer-Verlag Berlin Heidelberg 1998

Authors and Affiliations

  • Seiichiro Ten-no
    • 1
  1. 1.Institute for Molecular Science, Myodaiji, Okazaki, 444 JapanJP

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