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A density functional theory study of the molecular interactions between a series of amides and sulfuric acid

Ma, Xiaohui, Sun, Yanhui, Huang, Zixiao, Zhang, Qingzhu, Wang, Wenxing
Chemosphere 2019 v.214 pp. 781-790
Gibbs free energy, aerosols, ammonia, binding capacity, density functional theory, dimethylamine, dimethylformamide, evaporation rate, geometry, methylamine, pollutants, sulfuric acid
Amides, a class of nitrogen-containing organic pollutants in the atmosphere, may affect the formation of atmospheric aerosols by the interactions with sulfuric acid. Here, the molecular interactions of sulfuric acid with formamide, methylformamide, dimethylformamide, acetamide, methylacetamide and dimethylacetamide was investigated by density functional theory. Geometry optimization and Gibbs free energy calculation were carried out at M06-2X/6-311++G(3df,3pd) level. The results indicate that the addition of amides to H2SO4 might have a promoting effect on atmospheric new particle formation at 298.15 K and 1 atm. In the initial stage of new particle formation, the binding capacity of amides and sulfuric acid is stronger than ammonia, but weaker than methylamine. It is worth noting that the trans-methylacetamide could have similar capabilities of stabilizing sulfuric acid as dimethylamine. In the presence of water, amides are found to only have a weak enhancement capability on new particle formation. In addition, we can infer from evaporation rate that the small molecule clusters of formamide and sulfuric acid may be more energetically favorable than macromolecule clusters.