POTENTIAL-ENERGY FUNCTIONS OF POLYATOMIC-MOLECULES

A direct method is proposed for determining polyatomic potential energy functions, expressed in terms of normal coordinates, which yield a given set of vibrational excitation energies. The method is a modification of the semiclassical technique for computing vibrational energy levels of Percival and Pomphrey. The technique is used to derive potential functions for the NO2, SO2 and ClO2 molecules. With these potentials twenty two higher vibrational excitations energies have been predicted for these molecules and these results differ from the experimental values by at most 3 cm-1. The computed potential functions are not unique despite the apparent accuracy of the vibrational energy levels. Comparison with the RKR method indicates that the present method must be extended to include rotational perturbations. © 1979.