Rotational branching ratios and photoelectron angular distributions in resonance enhanced multiphoton ionization of diatomic molecules

In this paper we extend a previous formulation of molecular resonance enhanced multiphoton ionization (REMPI) photoelectron spectra to explicitly include multiplet‐specific final state wave functions and intermediate coupling schemes. The results of this formulation should be well suited and helpful in quantitative theoretical studies of rotationally resolved REMPI spectra in many diatomic molecules of interest. As an example, we use this formulation to study the rotational branching ratios and photoelectron angular distributions for (3+1) REMPI of NH via the 3 ^3Π Rydberg resonant state. The predicted anomalous rotational distributions are interpreted as arising from a Cooper minimum in the l=2 component of the kπ photoionization channel. A number of other results are obtained and discussed.