10.1007/s11449-008-1005-1

Abstract

The rotational Rydberg states of polar molecules, which arise as a result of the interaction of a Rydberg electron with core rotations, are considered. A large number of angular momenta in the core-electron system lead to a considerably greater number of possible coupling schemes of these momenta compared to the number of schemes determined by the classical five Hund’s cases for lower excited electron states of molecules. As a result of such detailed Hund’s classification, more than 30 different coupling schemes (Hund’s subcases) are constructed for rotational Rydberg states of molecules. The conditions of their realization are indicated in terms of the relative quantities of intramolecular interactions, for which analytical estimates are presented. For a large number of subcases, analytical expressions for the molecular matrix elements are found. These expressions can be useful in classification of the experimental spectra of highly excited molecules. As an application, for each of the subcases considered, analytical expressions are given, which describe the linear Zeeman effect and the Paschen-Back effect.