Stark Effect in Electronic Spectra: The Asymmetric Rotor

Abstract

Qualitative and quantitative analysis is made of the information obtainable from an electronic spectrum of an asymmetric rotor in an electric field. The most general case is considered where the Stark effect may be smaller, larger, or approximately equal to the asymmetry doubling. A method is described to obtain Stark‐asymmetric rotor energies and wavefunctions and from these determine the expected Stark‐effect patterns in optical spectra. It is shown that from these spectra one may obtain all three components of an excited‐state dipole moment, and its direction relative to the ground‐state moment. In addition, it is shown how the Stark effect may be used as an aid in the assignment of asymmetric rotor spectra.