Hermitian “chemical” Hamiltonian: an alternative ab initio method

Research output: Contribution to journalArticle

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Abstract

Some previous results of the present author are combined in order to develop a Hermitian version of the “Chemical Hamiltonian Approach.” In this framework the second quantized Born–Oppenheimer Hamiltonian is decomposed into one- and two-center components, if some finite basis corrections are omitted. (No changes are introduced into the one- and two-center integrals, while projective expansions are used for the three- and four-center ones, which become exact only in the limit of complete basis sets.) The total molecular energy calculated with this Hamiltonian can then presented as a sum of the intraatomic and diatomic energy terms which were introduced in our previous “chemical energy component analysis” scheme. The corresponding modified Hartree–Fock–Roothaan equations are also derived; they do not contain any three- and four-center integrals, while the non-empirical character of the theory is conserved. This scheme may be useful also as a “layer” in approaches like ONIOM.

Original languageEnglish
Article number86
JournalTheoretical Chemistry Accounts
Volume134
Issue number7
DOIs
Publication statusPublished - Jul 25 2015

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Hamiltonians
chemical energy
expansion
energy

Keywords

  • Alternative non-empirical SCF formalism
  • Chemical Hamiltonian Approach
  • Excluding three- and four-center integrals
  • Projective integral approximation
  • Second quantized Hamiltonian

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Hermitian “chemical” Hamiltonian : an alternative ab initio method. / Mayer, I.

In: Theoretical Chemistry Accounts, Vol. 134, No. 7, 86, 25.07.2015.

Research output: Contribution to journalArticle

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