Hermitian "chemical" Hamiltonian: an alternative ab initio method

Mayer, István (2015) Hermitian "chemical" Hamiltonian: an alternative ab initio method. THEORETICAL CHEMISTRY ACCOUNTS, 134 (7). p. 86. ISSN 1432-881X

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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.

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