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The PCILO Method

  • Jean-Paul Malrieu
Part of the Modern Theoretical Chemistry book series (MTC, volume 7)

Abstract

By all its basic concepts, the PCILO method(1–5) differs from the standard computational methods of quantum chemistry. Most methods are variational, while PCILO is a perturbation expansion. The large majority of ground-state calculations are performed in the Hartree-Fock independent-particle approximation, using an effective single-particle Hamiltonian, while PCILO works in a basis of N-electron wave functions, at the configuration interaction level, dealing with the total N-electron Hamiltonian. The molecular orbitals are frequently identified with the delocalized, symmetry-adapted MOs resulting from the diagonalization of the single-electron effective Hamiltonian, while the PCILO method refers to localized molecular orbitals describing chemical bonds and lone pairs. The first section of this chapter introduces these tools, and shows their connection with the more popular concepts of quantum chemistry. Section 2 contains the algorithm of the method, and Section 3 is a critical discussion of its validity and possible applications.

Keywords

Lone Pair Configuration Interaction Localize Determinant Atomic Integral Excited Determinant 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Plenum Press, New York 1977

Authors and Affiliations

  • Jean-Paul Malrieu
    • 1
  1. 1.Laboratoire de Physique QuantiqueUniversité Paul SabatierToulouseFrance

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