Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 8 2 2008 10.5194/acpd-8-7455-2008 http://www.atmos-chem-phys-discuss.net/8/7455/2008/ http://www.atmos-chem-phys-discuss.net/8/7455/2008/acpd-8-7455-2008.html http://www.atmos-chem-phys-discuss.net/8/7455/2008/acpd-8-7455-2008.pdf 7455 7476 2008-04-16 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, Department of Physical Sciences, 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. This implies that amines might be more important than ammonia in enhancing neutral and especially ion-induced sulfuric acid-water nucleation in the atmosphere. Ahlrichs, R., Bär, M., Häser, M., Horn, H., and Kölmel, C.: Electronic structure calculations on workstation computers: The program system Turbomole, Chem. Phys. Lett., 162, 165–169, 1989. Anttila, T., Vehkamäki, H., Napari, I., and Kulmala, M.: Effect of ammonium bisulphate formation on atmospheric water-sulphuric acid-ammonia nucleation, Boreal Environ. Res., 10, 511–523, 2005. Ball, S. M., Hanson, D. R., Eisele, F. L., and McMurry, P. H.: Laboratory studies of particle nucleation: Initial results for H₂SO₄, H₂O, and NH₃ vapors, J. Geophys. Res. D, 104, 23 709–23 718, 1999. Christiansen, O., Koch, H., and Jørgensen, P.: The second-order approximate coupled cluster singles and doubles model CC2, Chem. Phys. Lett., 243, 409–418, 1995. Dunning Jr., T. H., Peterson, K. A., and Wilson, A. K.: Gaussian basis sets for use in correlated molecular calculations. X. The atoms aluminum through argon revisited, J. Chem. Phys., 114, 9244–9253, 2001. Feller, A. D.: Application of systematic sequences of wave functions to the water dimer, J. Chem. Phys., 96, 6104–6114, 1992. Hunter, E. P. and Lias, S. G.: Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update, J. Phys. Chem. Ref. Data, 27, 413–656, 1998. Data available online via the NIST Chemistry WebBook. Häser, M. and Ahlrichs, R: Improvements on the direct SCF method, J. Comput. Chem., 10, 104–111, 1989. Korhonen, P., Kulmala, M., Laaksonen, A., Viisanen, Y., McGraw, R. and Seinfeld, J. H.: Ternary nucleation of H₂SO₄, NH₃, and H₂O in the atmosphere, J. Geophys. Res., 104, 26 349–26 353, 1999. Kulmala, M., Pirjola, L., and Mäkelä, J. M.: Stable sulphate clusters as a source of new atmospheric particles, Nature, 404, 66–69, 2000. Kulmala, M., Vehkamäki, H., Petäjä, T., Dal Maso, M., Lauri, A., Kerminen, V.-M., Birmili, W., and McMurry, P. H.: Formation and growth rates of ultrafine atmospheric particles: a review of observations, J. Aerosol. Sci., 35, 143–176, 2004a. Kulmala, M., Suni, T., Lehtinen, K. E. J., Dal Maso, M., Boy, M., Reissell, A., Rannik, Ãœ., Aalto, P., Keronen, P., Hakola, H., Bäck, J., Hoffmann, T., Vesala, T., and Hari, P.: A new feedback mechanism linking forests, aerosols, and climate, Atmos. Chem. Phys., 4, 557–562, 2004b. Kulmala, M., Riipinen, I., Sipilä, M., Manninen, H. E., Petäjä, T., Junninen, H., Dal Maso, M., Mordas, G., Mirme, A., Vana, M., Hirsikko, A., Laakso, L., Harrison, R. M., Hanson, I., Leung, C., Lehtinen, K. E. J., and Kerminen, V.-M.: Towards Direct Measurement of Atmospheric Nucleation, Science, 318, 89–92, 2007. Kurtén, T., Torpo, L., Ding, C.-G., Vehkamäki, H., Sundberg, M. R., Laasonen, K., and Kulmala, M.: A density functional study on water-sulfuric acid-ammonia clusters and implications for atmospheric cluster formation, Geophys. Res. 112, D04210, 2007a. Kurtén, T., Noppel, M., Vehkamäki, H., Salonen, M., and Kulmala, M.: Quantum chemical studies of hydrate formation of H₂SO₄ and HSO$_4^-$, Boreal Environ. Res., 12, 431–453, 2007b. Kurtén, T., Torpo, L., Sundberg, M. R., Vehkamäki, H., and Kulmala, M.: Estimation of the NH₃:H₂SO₄ ratio of nucleating clusters in atmospheric conditions using quantum chemical methods, Atmos. Chem. Phys., 7, 2765–2773, 2007c. Laakso, L., Grönholm, T., Kulmala, L., Haapanala, S., Hirsikko, A., Lovejoy, E. R., Kazil, J., Kurtén, T., Boy, M., Nilsson, E. D., Sogachev, A., Riipinen, I., Strattman, F., and Kulmala, M.: Hot-air balloon measurements of vertical variation of boundary layer new particle formation, Boreal Environ. Res., 12, 279–294, 2007. Lovejoy, E. R., Curtius, J., and Froyd, K. D.: Atmospheric ion-induced nucleation of sulfuric acid and water, J. Geophys. Res., 109, D08204, 2004. Mäkelä, J. M., Yli-Koivisto, S., Hiltunen, V., Seidl, W., Swietlicki, E., Teinilä, K., Sillanpää, M., Koponen, I. K., Paatero, J., Rosman, K., and Hämeri, K.: Chemical composition of aerosol during particle formation events in boreal forest, Tellus, 53B, 380–393, 2001. Murphy, S. M., Sorooshian, A., Kroll, J. H., Ng, N. L., Chhabra, P., Tong, C., Surratt, J. D., Knipping, E., Flagan, R. C., and Seinfeld, J. H: Secondary aerosol formation from atmospheric reactions of aliphatic amines, Atmos. Chem. Phys., 7, 2313–2337, 2007. Nadykto, A. B. and Yu, F.: Strong hydrogen bonding between atmospheric nucleation precursors and common organics, Chem. Phys. Lett., 435, 14–18, 2007. O'Dowd, C. D., Aalto, P., Hämeri, K., Kulmala, M. and Hoffmann, T.: Atmospheric particles from organic vapours, Nature, 416, 497–498, 2002. Ortega, I. K., Kurtén, T., Vehkamäki, H., and Kulmala, M.: The Role of Ammonia in Sulfuric Acid Ion-Induced Nucleation, Atmos. Chem. Phys. Discuss., 8, 5413–5436, 2008. Portmann, S.: MOLEKEL, Version 4.3.win32. Swiss Center for Scientific Computing (CSCS)/ETHZ, Switzerland, 2002. Rabaud, N. E., Ebeler, S. E., Ashbaugh, L. L., and Flocchini, R. G.: Characterization and quantification of odorous and non-odorous volatile organic compounds near a commercial dairy in California, Atmos. Environ., 37, 933–940, 2003. Schade, G. W. and Crutzen, P. J.: Emission of aliphatic amines from animal husbandry and their reactions: Potential source of N₂O and HCN, J. Atmos. Chem., 22, 319–346, 1995. Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, Wiley & Sons: New York, USA, 1998. Spracklen, D. V., Carslaw, K. S., Kulmala, M., Kerminen, V.-M., Mann, G. W., and Sihto, S.-L.: The contribution of boundary layer nucleation events to total particle concentrations on regional and global scales, Atmos. Chem. Phys., 6, 5631–5648, 2006. Torpo, L., Kurtén, T., Vehkamäki, H., Sundberg, M. R., Laasonen, K., and Kulmala, M.: The significant role of ammonia in atmospheric nanoclusters, J. Phys. Chem. A, 111, 10 671–10 674, 2007. Weigend, F. and Häser, M: RI-MP2: first derivatives and global consistency, Theor. Chem. Acc., 97, 331–340, 1997. Weigend, F., Häser, M., Patzelt, H., and Ahlrichs, R.: RI-MP2: Optimized auxiliary basis sets and demonstration of efficiency, Chem. Phys. Lett., 294, 143–152, 1998. Weigend, F., Köhn, A., and Hättig, C.: Efficient use of the correlation consistent basis sets in resolution of the identity MP2 calculations, J. Chem. Phys., 116, 3175–3183, 2002.