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

Abstract

Electronic spectroscopy of the 3 d Rydberg states of NO-Rg ( Rg = Ne , Ar , Kr , Xe ) van der Waals complexesThe laser induced fluorescence spectra of the thiohydroxyl radical inert gas complexes, R•SH ͑RϭNe, Ar, and Kr͒ are reported. The spectra of numerous isotopomers involving 32 S, 34 S, 84 Kr, 86 Kr, 1 H, and 2 H 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 2 ⌸ state and terminating on specific vibrational levels (v SH , v b k , v s ) of the à 2 ⌺ ϩ state, where nominally v s is the R-SH stretch, v SH is the SH monomer stretch, and v b k is the bending vibration. Vibrational frequencies, e , and anharmonicities, e x e , for many of the modes are obtained, as well as dissociation energies ͑assuming a simple model͒ for both the à and X states of the R•SH complexes.

Molecular Photodynamics in Rare Gas Solids

“…A similar stabilization is active for OH . This dramatic caging effect was verified for the SH−Ar complex, and through the analysis of high-resolution spectra, empirical potentials that embody the relevant physics have been extracted . In the more recent studies of H 2 S dissociation in matrixes, the spectroscopy of SH in Ne through Xe has been reanalyzed, drawing parallels between OH and SH .…”