ChemInform Abstract: GENERALIZED LOCALIZED ATOMIC ORBITALS

Abstract

Recent publications concerning localized atomic orbitals (LAOs) for atoms in closed shell molecules showed a number of LAO properties to be highly transferable insofar as the atom experienced equivalent bonding environments in a series of molecules. Assuming that transferability of LAO properties (such as interorbital angles and Mulliken populations) portends a concurrent transferability of LAO structure, we here deduce a set of average hybrids, or generalized LAOs (GLAOs). The GLAOs may, in principle, serve the same purpose as the familiar spn (n = 1, 2, 3,) orbitals; however, the former evidence a number of desireable trends not represented in the latter. For instance, GLAOs allow hybridization to vary in response to alterations in both degree of unsaturation (e.g., –C– vs C = vs = C = vs. –C≡) and atomic number (e.g., –C– vs. N– vs –O– vs F– ). This is in accord with experimental data such as bond angles, which tend to vary in conjunction with the same sorts of phenomena. It is important to note...