Electronic spectroscopy of the R⋅SH (R=Ne, Ar, Kr) complexes

The laser induced fluorescence spectra of the thiohydroxyl radical inert gas complexes, R⋅SH (R=Ne, Ar, and Kr) are reported. The spectra of numerous isotopomers involving 32S, 34S, 84Kr, 86Kr, 1H, and 2H have been observed. By using isotopic shifts of the heavy atoms, and other observations, the overwhelming majority of the 60 observed vibronic transitions have been assigned as originating from the vibrationless level of the X 2Π state and terminating on specific vibrational levels (vSH, vbk, vs) of the A 2Σ+ state, where nominally vs is the R-SH stretch, vSH is the SH monomer stretch, and vbk is the bending vibration. Vibrational frequencies, ωe, and anharmonicities, ωexe, for many of the modes are obtained, as well as dissociation energies (assuming a simple model) for both the A and X states of the R⋅SH complexes.