Rotationally resolved multiphoton ionization photoelectron spectroscopy of the [a ^1Δ]3dπ^2Φ and [a ^1Δ]5pπ^2Φ Rydberg states of the SH radical

Experimental and theoretical results on the rotationally resolved photoelectron spectra of the [a ^1Δ]3dπ^2Φ(v'=0) and the [a^ 1Δ]5pπ^2Φ(v'=0) Rydberg states of the SH radical are presented. In particular, for the former state, ionization via a large number of members of different rotational branches is considered. The interplay between experiment and ab initio calculations, including alignment, allows for a detailed interpretation of the results. Asymmetries apparent in the rotational ionic distributions and the observed suppression of transitions involving a large change in angular momentum can be explained on the basis of the theory.