A quantum chemical investigation of the mechanisms and kinetics of the reactions between methyl radical and n/i-propanol

Abstract

The mechanisms and kinetics of the reactions of methyl radical with n/i-propanol (n/i-C3H7OH) were investigated in detail using density functional theory and coupled cluster theory with rate constant prediction. The thermodynamic properties and the schematic potential energy surfaces of the two reactions were calculated by single point calculations at CCSD(T)/6–311++G(3df,2p) level based on geometries optimized at the B3LYP/6–311++G(3df,2p). The rate constants for various product channels of the two reactions in the temperature range of 298–2500 K were predicted by transition state theory and Eckart tunneling correction. The results of the analysis of schematic potential energy surfaces, thermokinetics parameters, and rate constants showed that the abstraction H-atom from the carbon atom which was bonded with an oxygen atom in the n/i-propanol molecules is the most favorable of these reaction systems.