Electronic Population Analysis on LCAO–MO Molecular Wave Functions. II. Overlap Populations, Bond Orders, and Covalent Bond Energies

Abstract

LCAO molecular orbital overlap populations give in general much more flexible and widely useful measures of the non-Coulombic parts of covalent bond energies than do LCAO bond orders. They are immediately applicable to both π and σ bonds, including bonds involving hybrid AOs of all kinds, and they take account directly of the effects of variations in bond length on bond strength. In the last section of this paper, a number of ways of defining LCAO bond orders are reviewed, and their advantages and disadvantages discussed. If all LCAO parameters β are assumed proportional to corresponding overlap integrals S times suitable mean atomic ionization energies Ī, a simple general approximate formula for covalent resonance energies is obtained in terms of partial overlap populations and Ī's, including one or two empirical coefficients. This formula indicates that forced hybridization (see III of this series) due to inner shells should make important negative contributions to bond energies. The application of the formula to H2, CO, and H2O is discussed. The assumption of proportionality of β values to SĪ values may be useful also in estimating unknown β values.