Applications of a simple molecular wavefunction. Part 10.—Analysis of the rotational barrier in hydrogen peroxide

Abstract

A study has been made of the rotational barriers in hydrogen peroxide using the simple FSGO molecular wavefunction proposed by Frost.

The barriers are analysed in terms of the components of the total molecular energy and also in terms of the contributions to the total electronic energy of single orthogonal Löwdin orbitals. It is found that it is necessary to optimise the molecular geometry for all dihedral angles if the correct changes in the energy components are to be obtained over the torsional potential energy surface. From the results presented, a physical interpretation of barrier formation is proposed. It is concluded that the shape of the potential energy curve is governed by the attractive and not the repulsive forces.