Abstract
Photochemistry of HSO2 isomers is studied by using FTIR spectroscopy in argon, krypton and xenon solids. Photodecomposition of H2S or H2O was used as a hydrogen atom source to study a diffusion controlled reaction of H and SO2. Mainly, the higher energy HSO2 isomer is formed in this reaction which is attributed to a low barrier for the HSO2 formation and a higher barrier for the formation of the lowest-energy species cis-HOSO. Photoexcitation of HSO2 at wavelengths below 580 nm promotes HSO2 → cis-HOSO interconversion. For this photoisomerisation two mechanisms are possible: direct isomerisation of HSO2 to cis-HOSO or a cage-induced reaction. The photodissociation threshold of cis-HOSO to H + SO2 is at 400 nm. The photon energies needed for these processes agree with the available computational data. To aid assignment of the experimental vibrational spectra, the equilibrium structures and the vibrational wavenumbers of HSO2, trans-HOSO, cis-HOSO and HXeOSO were calculated by ab initio methods.
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