Properties and Atmospheric Implication of Methylamine–Sulfuric Acid–Water Clusters

The presence of amines can increase aerosol formation rates. Most studies have been devoted to dimethylamine as the representative of amine; however, there have been a few works devoted to methylamine. In this study, theoretical calculations are performed on CH₃NH₂(H₂SO₄)_<i>m</i>(H₂O)_<i>n</i> (<i>m</i> = 0–3, <i>n</i> = 0–3) clusters. In addition to the structures and energetics, we focused on determining the following characteristics: (1) the growth mechanism, (2) the hydrate distributions and the influences of humidity and temperature, (3) Rayleigh scattering properties. We explored the cluster growth mechanism from a thermodynamics aspect by calculating the Gibbs free energy of adding a water or sulfuric acid molecule step by step at three atmospherically relevant temperatures. The relative ease of the reaction at each step is discussed. From the analysis of hydrate distributions, we find that CH₃NH₂(H₂SO₄)­(H₂O)₂, CH₃NH₂(H₂SO₄)₂, and CH₃NH₂(H₂SO₄)₃ are most likely to exist in the atmosphere. The general trend of hydration in all cases is more extensive with the growing relative humidity (RH), whereas the distributions do not significantly change with the temperature. Analysis of the Rayleigh scattering properties showed that both H₂SO₄ and H₂O molecules could increase the Rayleigh scattering intensities and isotropic mean polarizabilities, with greater influence by the sulfuric acid molecules. This work sheds light on the mechanism for further research on new particle formation (NPF) containing methylamine in the atmosphere