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Results of calculated and measuredphotoelectron spectra via the [a  ^1Δ]3dπ ^2Φ state of SH are reported. These spectra show a strong asymmetry away from classical expectations and only transitions up to ΔN=±2 are observed, in contrast to ΔN=±4 expected for photoionization of a 3dπ orbital. Agreement between the calculated and measured spectra is excellent.

Rotationally resolved photoelectron spectroscopy of the [a 1Δ]3dπ 2Φ Rydberg state of the SH radical