ESTIMATION OF GAS-PHASE HYDROXYL RADICAL RATE CONSTANTS OF OXYGENATEDCOMPOUNDS BASED ON MOLECULAR-ORBITAL CALCULATIONS

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