References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-7-2765-2007

Estimating the NH3:H2SO4 ratio of nucleating clusters in atmospheric conditions using quantum chemical methods

Kurtén

¹ Torpo

¹ Sundberg

M. R.

² Kerminen

V.-M.

³ Vehkamäki

¹ Kulmala

Division of Atmospheric Sciences, Department of Physical Sciences, P.O. Box 64, FI-00014 University of Helsinki, Finland

Laboratory of Inorganic Chemistry, Department of Chemistry, P.O. Box 55, FI-00014 University of Helsinki, Finland

Finnish Meteorological Institute, Air Quality Research, Sahaajankatu 20 E, FI-00880 Helsinki, Finland

25 05 2007

7 10 2765 2773

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We study the ammonia addition reactions of H2SO4·NH3 molecular clusters containing up to four ammonia and two sulfuric acid molecules using the ab initio method RI-MP2 (Resolution of Identity 2nd order Møller-Plesset perturbation theory). Together with results from previous studies, we use the computed values to estimate an upper limit for the ammonia content of small atmospheric clusters, without having to explicitly include water molecules in the quantum chemical simulations. Our results indicate that the NH3:H2SO4 mole ratio of small molecular clusters in typical atmospheric conditions is probably around 1:2. High ammonia concentrations or low temperatures may lead to the formation of ammonium bisulfate (1:1) clusters, but our results rule out the formation of ammonium sulfate clusters (2:1) anywhere in the atmosphere. A sensitivity analysis indicates that the qualitative conclusions of this study are not affected even by relatively large errors in the calculation of electronic energies or vibrational frequencies.

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