Journal of Molecular Modeling

, 21:238 | Cite as

Facet shapes and thermo-stabilities of H2SO4•HNO3 hydrates involved in polar stratospheric clouds

Original Paper
First Online:
Received:
Accepted:

Abstract

The nucleation, ice crystal shapes and thermodynamic stability of polar stratospheric clouds particles are interesting concerns owing to their implication in the ozone layer destruction. Some of these particles are formed by conformers of H2O, HNO3, and H2SO4. We carried out calculations using density functional theory (DFT) to obtain optimized structures. Several stable trimers are achieved —divided in two groups, one with HNO3 moiety, second with H2SO4 moiety— after pre-optimization at B3LYP/6-31G and subsequently optimization at B3LYP/aug-cc-pVTZ level of theory. For both most stable conformers five H2O molecules are added to their optimized trimers to calculate hydrated geometries. The OH stretching harmonic frequencies are provided for all aggregates. The zero-point energy correction (ZEPC), relative electronic energies (∆E), relative reaction Gibbs free energies ∆(∆G)k-relative, and cooling constant (K cooling ) are reported at three temperatures: 188 K, 195 K, and 210 K. Shapes given in our calculations are compared with various experimental shapes as well as comparisons with their thermo-stabilities.

Graphical Abstract

Facet shapes and thermo-stabilities of H2SO4•HNO3 hydrates involved in polar stratospheric clouds. IR spectrum of WNS-1+5W structure and its circular facet

Keywords

DFT B3LYP/aug-cc-pVTZ IR spectra Harmonic frequencies Structures Geometries Ice shapes Ice crystals Internal parameters Inter parameters Thermochemistry Thermostability Polar Stratospheric Clouds: PSCs Sulfuric acid hydrates Nitric acid hydrates Hydrates Cooling constant Gibbs free energy Electronic energy Relative Gibbs free energy Nitric acid Sulfuric acid Water hydrates Hexagonal crystals Pentagonal crystals Corone crystals Spherical crystals STS Supercooled Ternary solution 
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Supplementary material

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References

  1. 1.
    Kiang CS, Hamill P (1974) H2SO4/HNO3/H2O ternary system in the stratosphere. Nature 250:401–402CrossRefGoogle Scholar
  2. 2.
    Toon B, Pollack JB (1973) Physical properties of the stratosphere aerosols. J Geophys Res 78:7051–7056CrossRefGoogle Scholar
  3. 3.
    Adams RW, Downing HD (1986) Infrared optical constants of a ternary system of 75% H2SO4, 10% HNO3, and 15% H2O. J Opt Soc Am 3:22–28CrossRefGoogle Scholar
  4. 4.
    Reihs CM, Golden DV, Tolbert MA (1990) Nitric acid uptake by sulphuric acid solutions under stratospheric conditions: determination of Henry’s Law solubility. J Geophys Res 95:16545–16550CrossRefGoogle Scholar
  5. 5.
    Biermann UM, Luo BP, Peter T (2000) Absorption spectra and optical constants of binary and ternary solutions of H2SO4, HNO3, and H2O in the Mid infrared at atmospheric temperatures. J Phys Chem A 104:783–793CrossRefGoogle Scholar
  6. 6.
    Norman ML, Miller RE, Worsnop DR (2002) Ternary H2SO4/HNO3/H2O optical constants: new measurements from aerosol spectroscopy under stratospheric conditions. J Phys Chem A 106:6075–6083CrossRefGoogle Scholar
  7. 7.
    Lund Myhre CE, Grothe H, Gola AA, Nielsen CJ (2005) Optical constants of HNO3/H2O and H2SO4/HNO3/H2O at low temperatures in the infrared region. J Phys Chem A 109:7166–7171CrossRefGoogle Scholar
  8. 8.
    McPheat RA, Bass SF, Newnham DA, Ballard J, Remedios JJ (2002) Comparison of aerosol and thin film spectra of supercooled ternary solution aerosol. J Geophys Res 107(D19):4371. doi: 10.1029/2001JD000641 CrossRefGoogle Scholar
  9. 9.
    Wagner R, Mangold A, Möhler O, Saathoff H, Schnaiter M, Schurath U (2003) A quantitative test of infrared optical constants for supercooled sulphuric and nitric acid droplet aerosols. Atmos Chem Phys 3:1147–1164CrossRefGoogle Scholar
  10. 10.
    Fiacco DL, Hunt SW, Leopold KR (2002) Microwave investigation of sulfuric acid monohydrate. J Am Chem Soc 124:4504–4511CrossRefGoogle Scholar
  11. 11.
    Givan A, Larsen LA, Loewenschuss A, Nielsen CJ (1998) Infrared matrix isolation study of and its complexes H2SO4 with H2O. J Chem Soc Faraday Trans 94:827–835CrossRefGoogle Scholar
  12. 12.
    Rozenberg M, Loewenschuss A (2009) Matrix isolation infrared spectrum of the sulfuric acid-monohydrate complex: new assignments and resolution of the “missing H-bonded ν(OH) band” issue. J Phys Chem A 113:4963–4971CrossRefGoogle Scholar
  13. 13.
    Canagaratna M, Phillips JA, Ott ME, Leopold KR (1998) The nitric acid-water complex: microwave spectrum, structure, and tunneling. J Phys Chem A 102:1489–1497CrossRefGoogle Scholar
  14. 14.
    Meilinger SK, Koop T, Luo BP, Huthwelker T, Carslaw KS, Krieger U, Crutzen PJ, Peter T (1995) Size-dependent stratospheric droplets compositions in Lee wave temperature fluctuations and their potential role in PSC freezing. Geophys Res Lett 22:3031–3034CrossRefGoogle Scholar
  15. 15.
    Luo B, Krieger UK, Peter T (1996) Densities and refractive indices of H2SO4/HNO3/ H2O solutions to stratospheric temperatures. Geophys Res Lett 23:3707–3710CrossRefGoogle Scholar
  16. 16.
    Zhang R, Wooldridge PJ, Molina MJ (1993) Vapor pressure measurements for the H2SO4/HNO3/H2O and H2SO4/HCl/H2O systems: incorporation of stratospheric acids into background sulfate aerosols. J Phys Chem 97:8541–8548CrossRefGoogle Scholar
  17. 17.
    Molina MJ, Zhang R, Wooldridge PJ, McMahon JR, Kim JE, Chang HY, Beyer KD (1993) Physical chemistry of the H2SO4/HNO3/H2O system: implications for polar stratospheric clouds. Science 261:1418–1423CrossRefGoogle Scholar
  18. 18.
    Fox LE, Worsnop DR, Zahniser MS, Wofsy SC (1995) Metastable phases in polar stratospheric aerosols. Science 267:351–355CrossRefGoogle Scholar
  19. 19.
    Del Negro LA, Fahey DW, Donnelly SG, Gao RS, Keim ER, Wamsley RC, Woodbridge EL, Dye JE, Baumgardner D, Gandrud BW, Wilson JC, Josson HH, Loewenstein M, Podolske JR, Webster CR, May RD, Worsnop DR, Tabazadeh A, Tolbert MA, Kelly KK, Chan KR (1997) Evaluating the role of NAT, NAD, and liquid H2SO4/H2O/HNO3solutions in antarctic polar stratospheric cloud aerosol: observations and implications. J Geophys Res 102:13255–13282CrossRefGoogle Scholar
  20. 20.
    Hanson D, Mauersberguer K (1988) Laboratory studies of nitric acid trihydrate: implications for the south polar stratosphere. Geophys Res Lett 15:855–858CrossRefGoogle Scholar
  21. 21.
    Anthony SE, Onasch TB, Tisdale RT, Disselkamp RS, Tolbert MA (1997) Laboratory studies of ternary H2SO4/HNO3/H2O particles: implications for polar stratospheric cloud formation. J Geophys Res 102:10777–10784CrossRefGoogle Scholar
  22. 22.
    Koop T, Luo B, Biermann UM, Crutzen PJ, Peter T (1997) Freezing of HNO3/H2SO4/H2O solutions at stratospheric temperatures: nucleation, statistics and experiments. J Phys Chem A 101:1117–1133CrossRefGoogle Scholar
  23. 23.
    Chang AH-Y, Koop T, Molina LT, Molina MJ (1999) Phase transitions in emulsified HNO3/H2O and HNO3/H2SO4/H2O solutions. J Phys Chem A 103:2673–2679CrossRefGoogle Scholar
  24. 24.
    Koop T, Carslaw KS, Peter T (1997) Thermodynamic stability and phase transitions of PSC particles. Geophys Res Lett 24:2199–2202CrossRefGoogle Scholar
  25. 25.
    Headrick JM, Diken EG, Walters RS, Hammer NI, Christie RA, Cui J, Myshakin EM, Duncan MA, Johnson MA, Jordan KD (2005) Spectral signatures of hydrated proton vibrations in water clusters. Science 308:1765–1769CrossRefGoogle Scholar
  26. 26.
    Leopold KR (2011) Hydrated acid clusters. Annu Rev Phys Chem 62:327–349 and references 9-19 thereinCrossRefGoogle Scholar
  27. 27.
    Kjaergaard HG (2002) Calculated OH-Stretching vibrational transitions of the water-nitric acid complex. J Phys Chem A 106:2979–2987CrossRefGoogle Scholar
  28. 28.
    McCurdy PR, Hess WP, Xantheas SS (2002) Nitric acid-water complexes: theoretical calculations and comparison to experiment. J Phys Chem A 106:7628–7635CrossRefGoogle Scholar
  29. 29.
    Tóth G (1997) Quantum chemical study of the different forms of nitric acid monohydrate. J Phys Chem A 101:8871–8876CrossRefGoogle Scholar
  30. 30.
    Miller Y, Chaban GM, Gerber RB (2005) Theoretical study of anharmonic vibrational spectra of HNO3, HNO3-H2O, HNO4: fundamental, overtone and combination excitations. Chem Phys 313:213–224CrossRefGoogle Scholar
  31. 31.
    Kido Soule MC, Blower PG, Richmond GL (2007) Nonlinear vibrational spectroscopic studies of the adsorption and speciation of nitric acid at the vapor/acid solution interface. J Phys Chem A 111:3349–3357CrossRefGoogle Scholar
  32. 32.
    Miller Y, Chaban GM, Gerber RB (2005) Ab initio vibrational calculations for H2SO4 and H2SO4•H2O: spectroscopy and the nature of the anharmonic couplings. J Phys Chem A 109:6565–6574CrossRefGoogle Scholar
  33. 33.
    Arstila H, Laasonen K, Laaksonen A (1998) Ab initio study of gas-phase sulphuric acid hydrates containing 1 to 3 water molecules. J Chem Phys 108:1031–1039CrossRefGoogle Scholar
  34. 34.
    Al Natsheh A, Nadykto AB, Mikkelsen KV, Yu F, Ruuskanen J (2004) Sulfuric acid and sulfuric acid hydrates in the gas phase: a DFT investigation. J Phys Chem A 108:8914–8929CrossRefGoogle Scholar
  35. 35.
    Bandy AR, Ianni J (1998) Study of the Hydrates of H2SO4. J Phys Chem A 102:6533–6539CrossRefGoogle Scholar
  36. 36.
    Re S, Osamura Y, Morokuma K (1999) Coexistence of neutral and Ion-pair clusters of hydrated sulfuric acid H2SO4 (H2O)n (n = 1-5)— a molecular orbital study. J Phys Chem A 103:3535–3547CrossRefGoogle Scholar
  37. 37.
    Beichert P, Schrems O (1998) Complexes of sulfuric acid with hydrogen chloride, water, nitric acid, chloride nitrate and hydrogen peroxide: an ab initio investigation. J Phys Chem A 102:10540–10544CrossRefGoogle Scholar
  38. 38.
    Verdes M, Paniagua M (2014) Quantum chemical study of atmospheric aggregates: HCl•HNO3•H2SO4. J Mol Model 20:2232–2251CrossRefGoogle Scholar
  39. 39.
    Verdes M, Paniagua M (2015) Relative stabilities of HCl•H2SO4•HNO3 aggregates in polar stratospheric clouds. J Mol Model. doi: 10.1007/s00894-015-2611-7 Google Scholar
  40. 40.
    Givan A, Larsen LA, Loewnschuss A, Nielsen CJ (1999) Matrix isolation mid- and far-infrared spectra of sulfuric acid and deuterated sulfuric acid vapors. J Mol Struct 509:35–47CrossRefGoogle Scholar
  41. 41.
    Nadykto AB, Du H, Yu F (2007) Quantum DFT and DF-DFT study of vibrational spectra of sulfuric acid, sulfuric monohydrate, formic acid, and its cyclic dimer. Vib Spectrosc 44:286–296CrossRefGoogle Scholar
  42. 42.
    Yacovitch TI, Heine N, Brieger C, Wende T, Hock C, Neumark DM, Asmis KR (2013) Vibrational spectroscopy of bisufate/sulfuric acid/water clusters: structure, stability, and Infrared multiphase-photon dissociation intensities. J Phys Chem A 117:7081–7090CrossRefGoogle Scholar
  43. 43.
    Frisch GW,Trucks HB, Schlegel GE, Scuseria MA, Robb JR, Cheeseman G, Scalmani V, Barone B, Mennucci GA, Petersson H, Nakatsuji M, Caricato X, Li HP, Hratchian AF, Izmaylov J, Bloino G, Zheng JL, Sonnenberg M, Hada M, Ehara K, Toyota R, Fukuda J, Hasegawa M, Ishida T, Nakajima Y, Honda O, Kitao H, Nakai T, Vreven JA, Montgomery Jr JE, Peralta F, Ogliaro M, Bearpark JJ, Heyd E, Brothers KN, Kudin VN, Staroverov R, Kobayashi J, Normand K, Raghavachari A, Rendell JC, Burant SS, Iyengar J, Tomasi M, Cossi N, Rega JM, Millam M, Klene JE, Knox JB, Cross V, Bakken C, Adamo J, Jaramillo R, Gomperts RE, Stratmann O, Yazyev AJ, Austin R, Cammi C, Pomelli JW, Ochterski RL, Martin K, Morokuma VG, Zakrzewski GA, Voth P, Salvador JJ, Dannenberg S, Dapprich AD, Daniels O, Farkas JB, Foresman JV, Ortiz J, Cioslowski DJ, Fox MJ (2009) Gaussian 09, Revision A.02. Gaussian Inc, WallingfordGoogle Scholar
  44. 44.
    Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652CrossRefGoogle Scholar
  45. 45.
    Lee CT, Yang WT, Parr RG (1988) Development of the colle-salvetti correlation-energy formula into a functional of the electron-density. Phys Rev B 37:785–789CrossRefGoogle Scholar
  46. 46.
    Hehre WJ, Ditchfield R, Pople JA (1972) Self-consistent molecular orbital methods. XII. Further extensions of gaussian-type basis sets for Use in molecular orbital studies of organic molecules. J Chem Phys 56:2257–2261CrossRefGoogle Scholar
  47. 47.
    Dunning Jr TH (1989) Gaussian basis sets for use in correlated molecular calculations. J Chem Phys 90:1007–1023CrossRefGoogle Scholar
  48. 48.
    Kendall RA, Jr Dunning TH, Harrison RJ (1992) Electron affinities of the first-row atoms revisited systematic basis sets and wave functions. J Chem Phys 96:6796–6806CrossRefGoogle Scholar
  49. 49.
    Woon DE, Dunning Jr TH (1993) Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon. J Chem Phys 98:6796–6806CrossRefGoogle Scholar
  50. 50.
    Boys SF, Bernardi F (1970) Calculation of small molecular interactions by differences of separate total energies- same procedures with reduced errors. Mol Phys 19:553–566CrossRefGoogle Scholar
  51. 51.
    Lawless R, Xie Y, Yang P (2006) Polarization and effective Mueller matrix for multiple scattering of light by nonspherical ice crystals. Opt Express 14:6381–6393CrossRefGoogle Scholar
  52. 52.
    Noel V, Chepfer H, Ledanois G, Delaval A, Flamant H (2002) Classification of particle effective shape ratios in cirrus clouds based on the lidar depolarization ratio. Appl Opt 41:4245–4257CrossRefGoogle Scholar
  53. 53.
    Murray BJ, Malkin TL, Salzmann CG (2015) The crystal structure of ice under mesospheric conditions. J Atmos Sol Terr Physics. doi: 10.1016/j.jastp.2014.12.005i Google Scholar
  54. 54.
    Flatau PJ, Draine BT (2014) Light scattering by hexagonal columns in the discrete dipole approximation. Opt Express 22:21834–21846CrossRefGoogle Scholar
  55. 55.
    Borovoi A, Balin Y, Kokhanenko G, Penner I, Konoshonkin A, Kustova N (2014) Layers of quasi-horizontally oriented ice crystals in cirrus clouds observed by a two-wavelength polarization lidar. Opt Express 22:24566–24573CrossRefGoogle Scholar
  56. 56.
    Borovoi A, Konoshonkin A, Kustova N (2014) Backscatter ratios for arbitrary oriented hexagonal ice crystals of cirrus clouds. Opt Lett 39:5788–5791CrossRefGoogle Scholar
  57. 57.
    Järvinen E, Vochezer P, Möhler O, Schnaiter M (2014) Laboratory study of microphysical and scattering properties of corona-producing cirrus clouds. Appl Opt 53:7566–7575CrossRefGoogle Scholar
  58. 58.
    Marx D, Tuckerman ME, Hutter J, Parrinello M (1999) The nature of the hydrated excess proton in water. Nature 397:601–604CrossRefGoogle Scholar
  59. 59.
    Bogdan A, Molina MJ, Kulmala M, Tenhu H, Loerting T (2013) Solution coating around ice particles of incipient cirrus clouds. P.N.A.S. 110: 2439 and references thereinGoogle Scholar
  60. 60.
    Kuhs WF, Sippel CA, Falenty TC, Hansen (2013) Reply to Bogdan et al.: “Cubic ice” in cirrus clouds under dry and wet conditions. P.N.A.S. 110: 2440 and references thereinGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  1. 1.Departamento de Química Física Aplicada, Facultad de Ciencias, C-14Universidad Autónoma de MadridMadridSpain

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