Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 8 4 2008 10.5194/acpd-8-14497-2008 http://www.atmos-chem-phys-discuss.net/8/14497/2008/ http://www.atmos-chem-phys-discuss.net/8/14497/2008/acpd-8-14497-2008.html http://www.atmos-chem-phys-discuss.net/8/14497/2008/acpd-8-14497-2008.pdf 14497 14517 2008-07-30 Thermodynamics of homogeneous nucleation of ice particles in the polar summer mesosphere A. Y. Zasetsky S. V. Petelina s.petelina@latrobe.edu.au I. M. Svishchev Trent University, Peterborough, Ontario, Canada La Trobe University, Victoria, Australia formerly at: the University of Saskatchewan, Saskatoon, Canada We present the hypothesis of homogeneous nucleation of ice nano-particles in the polar summer mesosphere. The nucleation of condensed phase is traced back to the first step on the formation pathway, which is assumed to be the transition of water vapor to amorphous cluster. Amorphous clusters then freeze into water ice, likely metastable cubic ice, when they reach the critical size. The estimates based on the equilibrium thermodynamics give the critical size (radius) of amorphous water clusters as about 1.0 nm. The same estimates for the final transition step, that is the transformation of cubic to hexagonal ice, give the critical size of about 15 nm at typical upper mesospheric conditions during the polar summer (temperature T=150 K, water vapor density ρvapor=109 cm−3). Adams, G. W., Schmitt, J. L., and Zalabsky, R. A.: The Homogeneous nucleation of nonane, J. Chem. Phys., 81, 5074–5078, 1984. Allen, M. P. and Tildesley, D. J. : Computer Simulation of Liquids, Clarendon Press, Oxford, 385 pp., 1987. Bernath, P. F., McElroy, C. T., Abrams, M. C., Boone, C. D., Butler, M., Camy-Peyret, C., Carleer, M., Clerbaux, C., Coheur, P. F., Colin, R., DeCola, P., Bernath, P. F., McElroy, C. T., Abrams, M. C., Boone, C. D., Butler, M., Camy-Peyret, C., Carleer, M., Clerbaux, C., Coheur, P. F., Colin, R., DeCola, P., DeMaziere, M., Drummond,J. R., Dufour, D., Evans, W. F. J., Fast, H., Fussen, D., Gilbert, K., Jennings, D. E., Llewellyn, E. J., Lowe, R. P., Mahieu, E., McConnell, J. C., McHugh, M., Mcleod, S. D., Michaud, R., Midwinter, C., Nassar, R., Nichitiu, F., Nowlan, C., Rinsland, C. P., Rochon, Y. J., Rowlands, N., Semeniuk, K., Simon, P., Skelton, R., Sloan, J. J., Soucy, M. A., Strong, K., Tremblay, P., Turnbull, D., Walker, K. A., Walkty, I., Wardle, D. A., Wehrle, V., Zander, R., and Zou, J.: Atmospheric Chemistry Experiment (ACE): Mission overview, Geophys. Res. Lett., 32, L15S01, doi:10.1029/2005GL022386, 2005. Berendsen, H. J. C., Grigera, J. R., and Straatsma, T. P. J.: The missing term in effective pair potential, Phys. Chem., 91, 6269–6271, 1987. Boone, C. D., Nassar, R., Walker, K. A., Rochon, Y., Mcleod, S. D., Rinsland, C. P., and Bernath, P. F.: Retrievals for the atmospheric chemistry experiment Fourier-transform spectrometer, Appl. Optics, 44, 7218–7231, 8445, doi:10.1029/2002JD002398, 2005. Carleer,~M R., Boone,~C D., Walker,~K A., Bernath,~P F., Strong,~K., Sica,~R J., Randall,~C E., Vömel,~H., Kar,~J., Höpfner,~M., Milz,~M., von~Clarmann,~T., Kivi,~R., Valverde-Canossa,~J., Sioris,~C E., Izawa,~M R M., Dupuy,~E., McElroy,~C T., Drummond,~J R., Nowlan,~C R., Zou,~J., Nichitiu,~F., Lossow,~S., Urban,~J., Murtagh,~D., and Dufour,~D G.: Validation of water vapour profiles from the Atmospheric Chemistry Experiment (ACE), Atmos. Chem. Phys. Discuss., 8, 4499–4559, 2008. Deland, M. T., Shettle, E. P., Thomas, G. E., and Olivero, J. J.: Solar backscattered ultraviolet (SBUV) observations of polar mesospheric clouds (PMCs) over two solar cycles, J. Geophys. Res., 108(D8), 8445, doi:10.1029/2002JD002398, 2003. Devlin, J. P. and Buch, V.: Vibrational spectroscopy and modeling of the surface and subsurface of ice and of ice-adsorbate interactions, J. Phys. Chem., B, 101, 6095–6098, 1997. Devlin, J. P., Joyce, C., and Buch, V.: Infrared spectra and structures of large water clusters, J. Phys. Chem. A, 104, 1974–1977, 2000. Djikaev, Y. S., Tabazadeh, A., Hamill, P., and Reiss, H. J.: Thermodynamic conditions for the surface-stimulated crystallization of atmospheric droplets, J. Phys. Chem. A, 106, 10247, doi:10.1029/jp021044s, 2002. Eremenko, M. N., Petelina, S. V., Zasetsky, A. Y., Karlsson, B., Rinsland, C. P., Llewellyn, E. J., and Sloan, J. J.: Shape and composition of PMC particles derived from satellite remote sensing measurements, Geophys. Res. Lett., 32, L16S06, doi:10.1029/2005GL023013, 2005. Hale, B. N. and Plummer, P. L. M. : Molecular model for ice clusters in a supersaturated vapor, J. Chem. Phys., 61, 4012–4019, 1974. Hallbrucker, A., Mayer, E., and Johari, G. P.: Glass-liquid transition and the enthalpy of devitrification of annealed vapor-deposited amorphous solid water - a comparison with hyperquenched glassy water, J. Phys. Chem., 93, 4986–4990, 1989. Henson, B. F., Voss, L. F., Wilson, K. R., and Robinson, J. M.: Thermodynamic model of quasiliquid formation on H2O ice: Comparison with experiment, J. Chem. Phys., 123, 144707, doi:10.1063/1.2056541, 2005. Hruby, J. and Holten, V.: A two-structure model of thermodynamic properties and surface tension of supercooled water, 14th Conference on Properties of Water and Steam, Kyoto, 241–246, 2004. Johari, G. P.: Water's size-dependent freezing to cubic ice, J. Chem. Phys., 122, 194504, doi:10.1063/1.1900723, 2005. Laaksonen, A. and McGraw, R.: Thermodynamics, gas-liquid nucleation, and size-dependent surface tension, Europhys. Lett., 35, 367–372, 1996. Lide, R.: CRC Handbook of chemistry and physics, 80th Ed., CRC Press, Boca Raton, 2504 pp., 1999. Lübken, F.-J.: Thermal structure of the Arctic summer mesosphere, J. Geophys. Res., 104, 9135–9149, 1999. McGraw, R. and A. Laaksonen: Interfacial curvature free energy, the Kelvin relation, and vapor-liquid nucleation rate, J. Chem. Phys., 106, 5284–5287, 1997. Murphy, D. M. and T. Koop: Review of the vapour pressures of ice and supercooled water for atmospheric applications, Q. J. Roy.Meteorol. Soc., 131, 1539–1565, 2005. Nose, S.: A molecular dynamics method for simulations in the canonical ensemble, Mol. Phys., 52, 255–268, 1984. Ostwald, W.: Studien über die Bileding und Umwandlung fester Körper, Z. Phys. Chem., 22, 289, 1897. Petelina, S. V., Degenstein, D. A., Llewellyn, E. J., Lloyd, N. D., Mertens, C. J., Mlynczak, M. G., and Russell, J. M. : Thermal conditions for PMC existence derived from Odin/OSIRIS and TIMED/SABER data, Geophys. Res. Lett., 32, L17813, doi:10.1029/2005GL023099, 2005. Petelina, S. V., Llewellyn, E. J., and Degenstein, D. A.: Properties of polar mesospheric clouds measured by Odin/OSIRIS in the Northern Hemisphere in 2002–2005, Can. J. Phys., 85, 11, 1143–1158, 2007. Plane, J. M. C.: Atmospheric chemistry of meteoric metals, Chem. Rev., 103, 4963-4984, 2003. Plane, J. M. C., Murray, B. J., Chu, X. Z., and Gardner, C. S.: Removal of meteoric iron on polar mesospheric clouds, Science, 304, 426–428, 2004. Rapp, M. and Thomas, G. E.: Modeling the microphysics of mesospheric ice particles: Assessment of current capabilities and basic sensitivities, J. Atmos. Sol.-Terr. Phy., 68, 7, 715–744, 2006. Romero-Rochin, V. and Percus, J. K.: Stress tensor of liquid-vapor states of inhomogeneous fluids, Phys. Rev. E., 53, 5130–5136, 1996. Sica, R J., Izawa, M R M., Walker, K A., Boone, C., Petelina, S V., Argall, P S., Bernath, P., Burns, G B., Catoire, V., Collins, R L., Daffer, W H., De~Clercq, C., Fan, Z Y., Firanski, B J., French, W J R., Gerard, P., Gerding, M., Granville, J., Innis,J L., Keckhut, P., Kerzenmacher, T., Klekociuk, A R., Kyrö, E., Lambert, J C., Llewellyn, E J., Manney, G L., McDermid, I S., Mizutani, K., Murayama, Y., Piccolo, C., Raspollini, P., Ridolfi, M., Robert, C., Steinbrecht, W., Strawbridge, K B., Strong, K., Stübi, R., and Thurairajah, B.: Validation of the Atmospheric Chemistry Experiment (ACE) version 2.2 temperature using ground-based and space-borne measurements, Atmos. Chem. Phys., 8, 35–62, 2008. Speedy, R. J., Debenedetti, P. G., Smith, R. S., Huang, C., and Kay, B. D.: The evaporation rate, free energy, and entropy of amorphous water at 150 K, J. Chem. Phys., 105, 240–244, 1996. ten Wolde, P. R. and Frenkel, D.: Homogeneous nucleation and the Ostwald step rule, Phys. Chem. Chem. Phys., 1, 2191–2196, 1999. Thomas, G. E.: Mesospheric Clouds and the Physics of the Mesopause Region, Rev. Geophys., 29, 553–575, 1991. Viisanen, Y., Strey, R., and Reiss, H.: Homogeneous nucleation rates for water, J. Chem. Phys., 99, 4680–4692, 1993.