Atmospheric Chemistry and Physics Discussions
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2007
10.5194/acpd-7-2937-2007
http://www.atmos-chem-phys-discuss.net/7/2937/2007/
http://www.atmos-chem-phys-discuss.net/7/2937/2007/acpd-7-2937-2007.html
http://www.atmos-chem-phys-discuss.net/7/2937/2007/acpd-7-2937-2007.pdf
2937
2960
2007-02-23
Estimating the NH<sub>3</sub>:H<sub>2</sub>SO<sub>4</sub>ratio of nucleating clusters in atmospheric conditions using quantum chemical methods
T. Kurtén
theo.kurten@helsinki.fi
L. Torpo
M. R. Sundberg
V.-M. Kerminen
H. Vehkamäki
M. 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
We study the ammonia addition reactions of H<sub>2</sub>SO<sub>4</sub>·NH<sub>3</sub> 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 NH<sub>3</sub>:H<sub>2</sub>SO<sub>4</sub> 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.
Adams, P. J., Seinfeld, J. H., and Koch, D. M.: Global concentrations of tropospheric sulfate, nitrate, and ammonium aerosol simulated in a general circulation model, J. Geophys. Res., 104, D13791, 1999.
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 Env. 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 H<sub>2</sub>SO<sub>4</sub>, H<sub>2</sub>O, and NH<sub>3</sub> vapors, J. Geophys. Res. D, 104, 23 709–23 718, 1999.
Bandy, A. R. and Ianni, J. C.: Study of Hydrates of H<sub>2</sub>SO<sub>4</sub> Using Density Functional Theory, J. Phys. Chem. A, 102, 6533–6539, 1998.
Bates, T. S., Quinn, P. K., Coffman, D. J., Johnson, J. E., Miller, T. L., Covert, D. S., Wiedensohler, A., Leinert, S., Nowak, A., and Neususs, C.: Regional physical and chemical properties of the marine boundary layer aerosol across the Atlantic during Aerosols99: An overview, J. Geophys. Res. 106, 20 767–20 782, 2001.
Berglen, T. F., Berntsen, T. K, Isaksen, I. S. A., and Sundet, J. K.: A global model of the coupled sulfur/oxidant chemistry in the troposphere: The sulfur cycle. J. Geophys. Res., 109, D19310, doi:10.1029/2003JD003948, 2004.
Bouwman, A. F., Lee, D. S., Asman, W. A. H., Dentener, F. J., Van Der Hoek, K. W., and Olivier, J. G. J.: A global high-resolution emission inventory for ammonia, Global Biogeochem. Cycles, 11, 561–587, 1997.
Boys, S. F. and Bernardi, F: The Calculation of Small Molecular Interactions by the Differences of Separate Total Energies, Mol. Phys., 19, 553, 1970.
Clegg, S. L., Brimblecombe, P., and Wexler, A. S.: A thermodynamic model of the system H-NH<sub>4</sub>-SO<sub>4</sub>-NO<sub>3</sub>-H<sub>2</sub>O at tropospheric temperatures, J. Phys. Chem. A, 102, 2137–2154, 1998.
Ding, C.-G., Laasonen, K., and Laaksonen, A: Two Sulphuric Acids in Small Water Clusters, J.Phys. Chem A, 107, 8648–8658, 2003.
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.
Feng, Y. and Penner, J. E.: Global modeling of nitrate and ammonium: Interaction of aerosols and tropospheric chemistry, J. Geophys. Res., 112, D01304, doi:10.1029/2005JD006404, 2007.
Foresman, J. B. and Frisch, Ǽ: Exploring Chemistry with Electronic Structure Methods, 2nd edition, Gaussian, Inc., Wallingford CT, U.S.A., 1996.
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Montgomery, Jr., J. A., Vreven, T., Kudin, K. N., Burant, J. C., Millam, J. M., Iyengar, S. S., Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalmani, G., Rega, N., Petersson, G. A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J. E., Hratchian, H. P., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Ayala, P. Y., Morokuma, K., Voth, G. A., Salvador, P., Dannenberg, J. J., Zakrzewski, V. G., Dapprich, S., Daniels, A. D., Strain, M. C., Farkas, O., Malick, D. K., Rabuck, A. D., Raghavachari, K., Foresman, J. B., Ortiz, J. V., Cui, Q., Baboul, A. G., Clifford, S., Cioslowski, J., Stefanov, B. B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Martin, R. L., Fox, D. J., Keith, T., Al-Laham, M. A., Peng, C. Y., Nanayakkara, A., Challacombe, M., Gill, P. M. W., Johnson, B., Chen, W., Wong, M. W., Gonzalez, C., and Pople, J. A.: Gaussian 03, Revision C.02, Gaussian, Inc., Wallingford CT, 2004.
Hanson, D. R. and Eisele, F. L.: Diffusion of H<sub>2</sub>SO<sub>4</sub> in Humidified Nitrogen: Hydrated H<sub>2</sub>SO<sub>4</sub>, J. Phys. Chem. A, 104, 1715–1719, 2000.
Häser, M. and Ahlrichs, R: Improvements on the direct SCF method, J. Comput. Chem., 10, 104–111, 1989.
Helgaker, T., Klopper, W., Koch, H. and Noga. J.: Basis-set convergence of correlated calculations on water, Chem. Phys., 106, 9639–9646, 1997.
Ianni, J. C. and Bandy, A. R.: A theoretical study of the hydrates of (H<sub>2</sub>SO$_4)_2$ and its implications for the formation of new atmospheric particles, J. Mol. Struct (THEOCHEM), 497, 19–37, 2000.
Ianni, J. C. and Bandy, A. R.: A Density Functional Theory Study of the Hydrates of NH<sub>3</sub>*H<sub>2</sub>O*H<sub>2</sub>SO<sub>4</sub> and Its Implications for the Formation of New Atmospheric Particles, J. Phys. Chem. A, 103, 2801–2811, 1999.
Jensen, F.: Introduction to Computational Chemistry, 2nd edition, John Wiley & Sons, Ltd, West Sussex, UK, 2007.
Kettle, A. J. and Andreae, M. O.: Flux of dimethylsulfide from the oceans: A comparison of updated data sets and flux models, J. Geophys. Res., 105, 26 793–26 808, 2000.
Kulmala, M., Hämeri, K., Aalto, P. P., Mäkelä, J. M., Pirjola, L., Nilsson, E. D., Buzorius, G., Rannik, Ü., dal Maso, M., Seidl, W., Hoffman, T., Janson, R., Hansson, H.-C., Viisanen, Y., Laaksonen, A. and O'Dowd, C. D.: Overview of the international project on biogenic aerosol formation in the boreal forest (BIOFOR), Tellus, 53B, 324–343, 2001.
Kulmala, M., Lehtinen, K. E. J., Laakso, L., Mordas, G. and Hämeri, K.: On the existence of neutral atmospheric clusters, Boreal Env. Res., 10, 79–87, 2005.
Kurtén, T., Sundberg, M. R., Vehkamäki, H., Noppel, M., Blomqvist, J., and Kulmala, M.: An Ab Initio and Density Functional Theory Reinvestigation of Gas-Phase Sulfuric Acid Monohydrate and Ammonium Hydrogensulfate, J. Phys. Chem. A 110, 7178–7188, 2006.
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, J. Geophys. Res., in press, 2007.
Larson, L. J., Largent, A., and Tao, F.-M.: Structure of the sulfuric acid-ammonia system and the effect of water molecules in the gas phase, J. Phys. Chem. A., 103, 6786–6792, 1999.
Malm, W. C., Schichter, B. A., Pitchford, M. L., Ashbaugh, L. L., and Eldred, R. A.: Spatial and monthly trends in speciated fine particle concentration in the United States, J. Geophys. Res., 109, D03306, doi:10.1029/2003JD003739, 2004.
McMurry, P. H.: A review of atmospheric aerosol measurements, Atmos. Environ., 34, 1959–1999, 2000.
Møller, C. and Plesset, M. S.: Note on an Approximation Treatment for Many-Electron Systems, J. Phy. Rev., 46, 618–622, 1934.
Napari, I., Noppel, M., Vehkamäki, H. and Kulmala, M.: An improved model for ternary nucleation of sulfuric acid - ammonia - water, J. Chem. Phys., 116, 4221–4227, 2002.
Nash, D. G., Baer, T. and Johnson, M. V.: Aerosol mass spectrometry: An introductory review, Int. J. of Mass Spectrometry, 258, 2–12, 2006.
O'Dowd, C. D., Lowe, J. A., Smith, M. H., Davison, B., Hewitt, N., and Harrison, R. M.: (Biogenic sulphur emissions and inferred non-sea-salt-sulphate cloud condensation nuclei in and around Antrarctica, J. Geophys. Res., 102, 12 839–12 854, 1997.
Portmann, S.: MOLEKEL, Version 4.3.win32. Swiss Center for Scientific Computing (CSCS)/ETHZ, Switzerland, 2002.
Re, S., Osamura, Y., and Morokuma, K.: Coexistence of Neutral and Ion-Pair Clusters of Hydrated Sulfuric Acid (H<sub>2</sub>SO$_4)$(H<sub>2</sub>O)$_n$ (n= 1-5) – A Molecular Orbital Study, J. Phys. Chem. A, 103, 3535–3547, 1999.
Ricard, V., Jaffrezo, J.-L., Kerminen, V.-M., Hillamo, R. E., Sillanpää, M., Ruellan, S., Liousse, C., and Cachier, H.: Two years of continuous aerosol measurements in northern Finland, J. Geophys. Res., 107(D11), doi:10.1029/2001JD000952, 2002.
Riipinen, I., Sihto, S.-L., Kulmala, M., Arnold, F., Dal Maso, M., Birmili, W., Saarnio, K., Teinilä, K., Kerminen, V.-M., Laaksonen, A., and Lehtinen, K. E. J.: Connections between atmospheric sulphuric acid and new particle formation during QUEST III–IV campaigns in Heidelberg and Hyytiälä, Atmos. Chem. Phys. Discuss., 6, 10 837–10 882, 2006.
Schaap, M., Denier Van Der Gon, H. A. C., Dentener, F. J., Visschedijk, A. J. H., Van Loon, M., ten Brink, H. M., Putaud, J.-P., Guillaume, B., Liousse, C., and Builtjes, P. J. H.: Anthropogenic black carbon and fine aerosol distribution over Europe, J. Geophys. Res., 109, D18207, doi:10.1029/2003JD004330, 2004.
Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, Wiley&Sons: New York, U.S.A, 1998.
Vehkamäki, H., Napari, I., Kulmala M., and Noppel, M: Stable ammonium bisulphate clusters in the atmosphere, Phys. Rev. Lett., 93, 148501-1–148501-4, 2004.
Virkkula, A., Teinilä, K., Kerminen, V.-M., Saarikoski, S., Aurela, M., Viidanoja, J., Paatero, J., Koponen, I. K., and Kulmala, M.: Chemical composition of boundary layer aerosol over Atlantic Ocean and at an Antarctic site, Atmos. Chem. Phys. 6, 3407–3421, 2006.
Wavefunction, Inc: Spartan '02 Windows, Wavefunction, Inc. Irvine, CA, U.S.A., 2002. See also: http://www.wavefun.com.
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.