Theoretical study of the cis-pinonic acid and its atmospheric hydrolysate participation in the atmospheric nucleation

摘要

cis-Pinonic acid (CPA), one of the major photooxidation products of alpha-pinene, is believed to contribute to the formation of aerosols formed over forested areas. In the current study, we implement quantum chemical calculation to investigate the interaction between sulfuric acid (SA) and CPA as well as the hydrolysate of CPA (HCPA) in the presence of water or ammonia in the atmosphere. The lowest free energy configurations, reactants, transition states, intermediates, and products were optimized at 298/278 K and 1 atm at the M06-2X/6-311+G(3df,3pd) level. Our results show that one CPA molecule might initially nucleate with SA molecules and subsequently participate in the formation and growth of the new particle in the form of HCPA. More than one HCPA molecule may be involved in the critical nuclei. Furthermore, the hydrolysis reaction of CPA can be effectively catalyzed by SA and nitric acid (NA) in presence of water, which significantly increases the HCPA content in the atmosphere and subsequently promotes the particle nucleation. Overall, the current study elucidates a new mechanism of atmospheric nucleation driven by CPA and its hydrolysate. (C) 2019 Published by Elsevier B.V.