Localized Atomic and Molecular Orbitals. II

• DOI: 10.1063/1.1701520
• Publication Date: 2005-01-09T08:01:39Z
• Authors: Clyde Edmiston; Klaus Ruedenberg
• Keywords: Localized molecular orbitals; Slater-type orbital; Natural bond orbital; Molecular orbital diagram; STO-nG basis sets; Cubic harmonic; Orbital hybridisation

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