The Virial and Molecular Structure

Abstract

The virial theorem can be applied to a molecule, assuming that external forces are applied to keep the nuclei fixed. The mean electronic kinetic energy is then the negative of the mean total internal energy, plus a term arising from the virial of the external force. Since the external force is derivable from the knowledge of the total internal energy as function of nuclear position, this theorem gives a means of finding kinetic and potential energy separately for all configurations of the nuclei, as soon as the total energy is known, from experiment or theory. By using simple forms of curve for total energy, for the diatomic molecule, the kinetic and potential energy are derived and discussed. The curves give direct indication of the formation of the covalent bond, in cases where this occurs, by describing the removal of charge from the atoms to the region between the atoms, with resulting decrease of kinetic energy, increase of potential energy.