Results of calculated and measured photoelectron spectra via the [a1Δ]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.

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