A New Theoretical Method for the Accurate Calculation of Expectation Values on Fuctions of Internuclear Separation in Singlet sigma-State Diatomic Molecules

摘要

A new theoretical method for the calculation of expectation values on singlet Sigma-state diatomic molecular vibration-rotation states is developed. Using Dunham's theory of vibration-rotation energies, each integral can be expressed as a rapidly converging series of terms, each of which is given to high accuracy as an analytical function of the internuclear potential parameters. Results are presented which allow the rapid calculation of expectation values on any arbitrarily specified algebraic function of intermolecular separation, complete to four orders in the ratio of the rotational to vibrational constant of the molecule. The method is applied to a review and extension of the theoretical calculation of rotational energies in H2.