Energetics of mechanism of OH-propene reaction at low pressures in inert atmosphere

Abstract

MP2 calculations with full geometry optimizations were performed with a double- and a triple-zeta basis set to obtain the energy profile for reactions of propene + OH and ethene + OH at low pressures. In these conditions, the β-hydroxyalkyl radicals formed after OH addition to the alkene double bond may go through a rearrangement reaction to form easily identifiable aldehydes and ketones. The theoretical results obtained reproduce the available experimental data well and shed light on the mechanism of reactions characterized by negative activation energies. © 1998 John Wiley & Sons, Inc.