Localized Atomic and Molecular Orbitals. II

Publisher Website
Google Scholar
Abstract
Using a recently proposed procedure, the localized molecular orbitals are determined for minimal‐basis‐set LCAO—SCF wavefunctions of the molecules LiH, BH, NH, FH, Li2, B2, Be2, N2, F2, CO, BF, LiF. In all cases, well‐defined inner‐shell, lone‐pair, and bond orbitals are found. They exhibit a considerable degree of transferability between different molecules, and the s‐p hybridization varies regularly across the periodic table. In some cases the localized molecular orbitals deviate from accepted intuition; in all cases the exact determination of intrasymmetry localization is important. A close relation is found between the localized molecular orbitals and those molecular orbitals which extremize the MO‐overlap populations. In the case of the HF molecule, the localized orbitals are also determined for the exact self‐consistent‐field wavefunction and, the transformation from canonical to localized molecular orbitals is found to be almost identical with that in the minimal‐basis‐set approximation. Implications of the localization procedures and its results are discussed.

This publication has 11 references indexed in Scilit: