Quasi-classical trajectory and direct-dynamics CVT study on the initiation steps of methanol combustion

Abstract

Direct-dynamics canonical variational transition-state theory (CVT) and quasi-classical trajectory (QCT) calculations have been performed to study the dynamics of the initiation steps in the methanol combustion at high oxygen concentration. The initiation steps in combustion of methanol is hydrogen abstraction from carbon or oxygen in methanol to produce hydroxymethyl radical (CH2OH) or methoxy radical (CH3O), respectively, and hydroperoxyl radical (HO2). A new analytical potential energy function driven from our DFT calculations is constructed to study the dynamics of the title reactions. Reactive cross sections and reaction probabilities at various relative translational energies and initial vibrational and rotational reactant excitation were obtained to calculate the rate constants. The calculated rate constants from CVT and QCT calculations are compared.