TY - JOUR
T1 - Clustering mechanism of oxocarboxylic acids involving hydration reaction
T2 - Implications for the atmospheric models
AU - Liu, Ling
AU - Kupiainen-Määttä, Oona
AU - Zhang, Haijie
AU - Li, Hao
AU - Zhong, Jie
AU - Kurtén, Theo
AU - Vehkamäki, Hanna
AU - Zhang, Shaowen
AU - Zhang, Yunhong
AU - Ge, Maofa
AU - Zhang, Xiuhui
AU - Li, Zesheng
N1 - Publisher Copyright:
© 2018 Author(s).
PY - 2018/6/7
Y1 - 2018/6/7
N2 - The formation of atmospheric aerosol particles from condensable gases is a dominant source of particulate matter in the boundary layer, but the mechanism is still ambiguous. During the clustering process, precursors with different reactivities can induce various chemical reactions in addition to the formation of hydrogen bonds. However, the clustering mechanism involving chemical reactions is rarely considered in most of the nucleation process models. Oxocarboxylic acids are common compositions of secondary organic aerosol, but the role of oxocarboxylic acids in secondary organic aerosol formation is still not fully understood. In this paper, glyoxylic acid, the simplest and the most abundant atmospheric oxocarboxylic acid, has been selected as a representative example of oxocarboxylic acids in order to study the clustering mechanism involving hydration reactions using density functional theory combined with the Atmospheric Clusters Dynamic Code. The hydration reaction of glyoxylic acid can occur either in the gas phase or during the clustering process. Under atmospheric conditions, the total conversion ratio of glyoxylic acid to its hydration reaction product (2,2-dihydroxyacetic acid) in both gas phase and clusters can be up to 85%, and the product can further participate in the clustering process. The differences in cluster structures and properties induced by the hydration reaction lead to significant differences in cluster formation rates and pathways at relatively low temperatures.
AB - The formation of atmospheric aerosol particles from condensable gases is a dominant source of particulate matter in the boundary layer, but the mechanism is still ambiguous. During the clustering process, precursors with different reactivities can induce various chemical reactions in addition to the formation of hydrogen bonds. However, the clustering mechanism involving chemical reactions is rarely considered in most of the nucleation process models. Oxocarboxylic acids are common compositions of secondary organic aerosol, but the role of oxocarboxylic acids in secondary organic aerosol formation is still not fully understood. In this paper, glyoxylic acid, the simplest and the most abundant atmospheric oxocarboxylic acid, has been selected as a representative example of oxocarboxylic acids in order to study the clustering mechanism involving hydration reactions using density functional theory combined with the Atmospheric Clusters Dynamic Code. The hydration reaction of glyoxylic acid can occur either in the gas phase or during the clustering process. Under atmospheric conditions, the total conversion ratio of glyoxylic acid to its hydration reaction product (2,2-dihydroxyacetic acid) in both gas phase and clusters can be up to 85%, and the product can further participate in the clustering process. The differences in cluster structures and properties induced by the hydration reaction lead to significant differences in cluster formation rates and pathways at relatively low temperatures.
UR - http://www.scopus.com/inward/record.url?scp=85048204439&partnerID=8YFLogxK
U2 - 10.1063/1.5030665
DO - 10.1063/1.5030665
M3 - Article
C2 - 29884029
AN - SCOPUS:85048204439
SN - 0021-9606
VL - 148
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 21
M1 - 214303
ER -