Radiative relaxation and fragmentation dynamics of S 2p-excited hydrogen sulfide

Radiative relaxation of S 2p-excited hydrogen sulfide (H(2)S) is investigated by dispersed ultraviolet and visible fluorescence spectroscopies. We observe distinct changes in the fluorescence spectra as a function of excitation energy. Excitation to Rydberg states below the S 2p ionization threshold yields intense fluorescence from neutral and ionic atomic fragments (H, S(+), and S(2+)). In addition to the atomic emission, fluorescence of the molecular fragment ion HS(+) is preferably found after excitation of the S 2p electron into the unoccupied 6a(1) and 3b(2) orbitals with sigma(*) character. This is interpreted as evidence for ultrafast dissociation of the core-excited molecule prior to electronic relaxation. The rotationally resolved fluorescence spectra of the A (3)Pi-->X (3)Sigma(-) transition are analyzed in terms of the fragmentation dynamics leading to the formation of the excited molecular fragment ion, where changes in bond angle are discussed in terms of the rotational population.