HSO2 isomers in rare-gas solids

Literature Information

Publication Date 2002-03-21
DOI 10.1039/B110109A
Impact Factor 3.676
Authors

Esa Isoniemi, Leonid Khriachtchev, Jan Lundell, Markku Räsänen


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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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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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