Journal article

Unimolecular reaction chemistry of a charge-tagged beta-hydroxyperoxyl radical

Sui So, Benjamin B Kirk, Adam J Trevitt, Uta Wille, Stephen J Blanksby, Gabriel da Silva

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | ROYAL SOC CHEMISTRY | Published : 2014

Abstract

β-Hydroxyperoxyl radicals are formed during atmospheric oxidation of unsaturated volatile organic compounds such as isoprene. They are intermediates in the combustion of alcohols. In these environments the unimolecular isomerization and decomposition of β-hydroxyperoxyl radicals may be of importance, either through chemical or thermal activation. We have used ion-trap mass spectrometry to generate the distonic charge-tagged β-hydroxyalkyl radical anion, ˙CH2C(OH)(CH3)CH2C(O)O(-), and investigated its subsequent reaction with O2 in the gas phase under conditions that are devoid of complicating radical-radical reactions. Quantum chemical calculations and master equation/RRKM theory modeling ar..

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