Abstract
The Rydberg states of high n belonging to series converging to an ion state with a nonzero spin–orbit splitting must be described in so‐called Hund’s case (e). The derivation of the wave function obtained by transition from case (a) to case (e) is given. Application is made for a 2Π ionic core. This scheme is particularly useful to understand, for example, rotationally resolved spin–orbit autoionization.