Premium
From atomic and molecular orbitals to chemical orbitals
Author(s) -
Clementi Enrico,
Corongiu Giorgina
Publication year - 2008
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21614
Subject(s) - valence bond theory , atomic orbital , wave function , slater type orbital , molecular orbital , molecular orbital theory , modern valence bond theory , atomic physics , orbital hybridisation , linear combination of atomic orbitals , chemistry , basis set , generalized valence bond , valence (chemistry) , molecular orbital diagram , ionic bonding , physics , molecular physics , electron , quantum mechanics , molecule , ion
In this work, we analyze the molecular orbitals (MO) one‐electron functions of the Hartree‐Fock (HF) model and the atomic orbitals (AO) of the Heitler‐London (HL) and valence bond (VB) models. The complementarity of MO with AO orbitals has been evidenced with the recent Hartree‐Fock‐Heitler‐London model. We propose a new and general one‐electron function, the chemical orbital (CO) and the corresponding determinantal wave function, the chemical orbital wave function, Ψ CO . We show that the Ψ CO can be decomposed into a specific HF‐HL function with ionic components, designated “adjoined HF‐HL function” and that the HF‐HL, HF, and VB wave functions can be derived from the Ψ CO wave function. A single “adjoined HF‐HL function” can realistically represent molecular systems from the united atom, to equilibrium distances, to dissociation; short linear expansions of “adjoined HF‐HL functions” yield accurate nonrelativistic energies. Preliminary test computations with “adjoined HF‐HL functions” are presented for the ground state of the H 2 and LiH molecules © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008