Penning ionization electron spectroscopy of hydrogen sulfide by metastable helium and neon atoms

The dynamics of the Penning ionization of hydrogen sulfide molecules by collision with helium and metastable neon atoms, occurring in the thermal energy range, has been studied by analyzing the energy spectra of the emitted electrons obtained in our laboratory in a crossed beam experiment. These spectra are compared with the photoelectron spectra measured by using He(I) and Ne(I) photons under the same experimental conditions. In this way we obtained the negative energy shifts for the formation of H2S(+) ions in the first three accessible electronic states by He*(2(3,1)S1,0) and Ne*((3)P2,0) Penning ionization collisions: the 2b1 (X̃(2)B1) fundamental one, the first 5a1 (Ã(2)A1), and the second 2b2 (B̃(2)B2) excited states, respectively. The recorded energy shifts indicate that in the case of He* and Ne*-H2S the autoionization dynamics depends on the features of the collision complex and is mainly driven by an effective global attraction that comes from a balance among several non covalent intermolecular interaction components. This suggests that the Penning ionization should take place, in a specific range of intermolecular distances, as we have already observed in the case of Penning ionization of water molecules [Brunetti, B. G.; Candori, P.; Falcinelli, S.; Pirani, F.; Vecchiocattivi, F. J. Chem. Phys. 2013, 139, 164305-1-164305-8].