Capture of the Sulfur Monoxide–Hydroxyl Radical Complex
Changyun Chen, Bo Lü, Xiaofang Zhao, Weiyu Qian, Jie Liu, Tarek Trabelsi, Joseph S. Francisco, Jie Qin, Jun Li, Lina Wang, Xiaoqing Zeng
Abstract
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.
Topics & Concepts
ChemistryHydroxyl radicalSulfurCarbon monoxideSulfur dioxideRadicalPhotochemistryOrganic chemistryCatalysisFree Radicals and AntioxidantsAtmospheric chemistry and aerosolsCrystallography and molecular interactions