Inverse perturbation analysis: Improving the accuracy of potential energy curves

Abstract

The equation for the first-order energy correction is used inversely to find the perturbation responsible for the energy correction. In the specific application to the calculation of a potential energy curve from the spectroscopic term values, the sought perturbation is a correction to an approximate potential curve. Consequently, an approximate potential curve (e.g. an RKR (Rydberg-Klein-Rees) curve) can be improved until the eigenvalues calculated for this curve agree with the spectroscopic term values within the experimental uncertainty. Results are given for the X 2Σ + state of HgH.