Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 8 14 2008 10.5194/acp-8-4095-2008 http://www.atmos-chem-phys.net/8/4095/2008/ http://www.atmos-chem-phys.net/8/4095/2008/acp-8-4095-2008.html http://www.atmos-chem-phys.net/8/4095/2008/acp-8-4095-2008.pdf 4095 4103 2008-07-30 Amines are likely to enhance neutral and ion-induced sulfuric acid-water nucleation in the atmosphere more effectively than ammonia T. Kurtén theo.kurten@helsinki.fi V. Loukonen H. Vehkamäki M. Kulmala Division of Atmospheric Sciences and Geophysics, Dept. of Physics, P.O.Box 64, 00014 University of Helsinki, Finland We have studied the structure and formation thermodynamics of dimer clusters containing H₂SO₄ or HSO₄^− together with ammonia and seven different amines possibly present in the atmosphere, using the high-level ab initio methods RI-MP2 and RI-CC2. As expected from e.g. proton affinity data, the binding of all studied amine-H₂SO₄ complexes is significantly stronger than that of NH₃•H₂SO₄, while most amine-HSO₄^− complexes are only somewhat more strongly bound than NH₃•HSO₄^−. Further calculations on larger cluster structures containing dimethylamine or ammonia together with two H₂SO₄ molecules or one H₂SO₄ molecule and one HSO₄^− ion demonstrate that amines, unlike ammonia, significantly assist the growth of not only neutral but also ionic clusters along the H₂SO₄ co-ordinate. A sensitivity analysis indicates that the difference in complexation free energies for amine- and ammonia-containing clusters is large enough to overcome the mass-balance effect caused by the fact that the concentration of amines in the atmosphere is probably 2 or 3 orders of magnitude lower than that of ammonia. 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