Estimation of gas-phase hydroxyl radical rate constants of oxygenated compounds based on molecular orbital calculations

In the molecular orbital based estimation method for gas-phase hydroxyl radical rate constants MOOH so far most oxygenated organic compounds have been excluded due to indications for reaction mechanisms different from direct H-abstraction or OH-addition to double or aromatic bonds. In the present article we give an extension of the approach to ketones, alcohols, ethers, carbonic acids and aldehydes. The basic mechanistic assumption for these oxygenated compounds is an addition step of the hydroxyl radical to the oxygen lone-pairs prior to the H-abstraction. Finally an extension to alkynes is given.