Theoretical study on the chemical formation mechanism of a β-myrcene ozonolysis reaction under atmospheric conditions

Author： Bai Jing Zhang Chenxi Gong Chen Sun Xiaomin

ISSN： 1480-3291

Source： Canadian Journal of Chemistry, Vol.90, Iss.8, 2012-08, pp. : 708-715

Disclaimer: Any content in publications that violate the sovereignty, the constitution or regulations of the PRC is not accepted or approved by CNPIEC.

Previous Menu Next

Abstract

Density functional theory (DFT) was used to study the β-myrcene ozonolysis reaction. The reactants, intermediates, transition states, and products were optimized at the MPWB1K/6–31G(d,p) level. The single-point energies were performed at the MPWB1K/6–311+G(3df,2p) level. The profiles of the potential energy surfaces were constructed and the rate constants of the reaction steps were analyzed. The possible reaction mechanisms for the ozonolysis intermediates in real atmosphere are also discussed. Based on quantum chemistry information, the rate constants were calculated using Rice–Ramsperger–Kassel–Marcus (RRKM) theory and the canonical variational transition-state theory (CVT) with small curvature tunneling effect (SCT). Arrhenius equations of rate constants over the temperature range of 200–800 K are provided, and the lifetimes of the reaction species in the troposphere were estimated according to rate constants.