A localized molecular orbital study of the structure and bonding of ozone

Abstract

The localized molecular orbital theory and energy partitioning formalism have been invoked to study the structure and bonding in ozone molecule. The range of investigation covers a large number of conformations generated theoretically over the wide range of apical angles between angular (<i>C_2v</i>) to linear (<i>D_∞h</i>) shapes. The results demonstrate that, similar to the

bonding in diborane, there are two equivalent three-centered bonds in ozone embracing three oxygen atoms in all the conformations. The possibility of a triangular structure of ozone is ruled out because the computed localized molecular orbitals demonstrate that there is no bonding between the terminal oxygen atoms and the decomposed energy components

show that the interaction between terminal oxygen atoms is strongly repulsive. Charge density distribution is asymmetric in the homonuclear molecule and its dipole moment is an algebraic sum of bond moment and lone pair moment and lone pair on the apical oxygen atom contributes significantly to the dipole moment. It is demonstrated that any attempt of calculating the apical angle from the experimentally determined dipole moment would be erroneous and misleading. Variation of dipole moment as a function of angular to linear reorganization of molecular shape is correlated in terms of computed quantum mechanical hybridization of the lone pair on the apical oxygen atom. The barrier to in version of ozone through the linear (<i>D_∞h</i>) transition state originates from a subtle interplay of one- and two- center energy components over the entire skeleton of the molecule.