A density functional theory study of aldehydes and their atmospheric products participating in nucleation. Issue 2 (13th December 2017)

• Record Type: Journal Article
• Authors: Shi, Xiangli; Zhang, Ruiming; Sun, Yanhui; Xu, Fei; Zhang, Qingzhu; Wang, Wenxing
• Is Part Of: Physical chemistry chemical physics. Volume 20:Issue 2(2017)
• Page Start: 1005
• Page End: 1011
• Publication Date: 2017-12-13
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c7cp06226e
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The products of aldehydes from aldol condensation, hydration, and polymerization reactions can promote new particle formation by stabilizing sulfuric acid. Abstract : Aldehydes have been speculated as important precursor species in the formation of new atmospheric particles. In the present work, quantum chemical calculations were performed to investigate the hydrogen bonding interaction and the Gibbs free energy of formation (Δ G ) for clusters consisting of sulfuric acid and aldehydes as well as their atmospheric reaction products. Calculations were conducted at 298 K and 1 atm at the M06-2X/6-311+G(3df, 3pd) level. The results show that the addition of aldehyde compounds to H2 SO4 unlikely contributes to new particle formation. However, their products from aldol condensation, hydration, and polymerization reactions can promote new particle formation by stabilizing sulfuric acid in the first step of nucleation. Moreover, the favorability of the interaction in the absence of water between sulfuric acid and the addition products is as follows: the hydration products > aldol condensation > aldehydes, but the results may be changed if water molecules are added. In particular, the calculated Δ G values imply that the monohydrate of glyoxal is more likely to nucleate with H2 SO4 in comparison with ammonia in the presence or absence of water.