The
elusive hydrogen-bonded sulfur monoxide–hydroxyl radical
complex (•OH···OS), a missing intermediate in
the atmospheric chemistry of SO2, was generated in the
266 nm laser photolysis of the sulfinyl radical HOSO• in cryogenic
Ar-matrixes. In addition to the IR spectroscopic characterization
with deuteration, its thermal conversion to HOSO• with an activation
barrier of 0.33 ± 0.11 kcal mol–1 (calcd 0.32
kcal mol–1, CCSD(T)-F12a/AVTZ) in the temperature
range of 15.0–21.0 K and a H/D kinetic isotope effect of 2.4
at 16.0 K have been observed.
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