Model molecular dynamics simulation of hydrochloric acid ionization at the surface of stratospheric ice

Abstract

The issue of the acid ionization of HCl at the surface of stratospheric ice particles, which is relevant in connection with Antarctic stratospheric ozone depletion, is studied theoretically. This study extends that of Gertner and Hynes (Science, 1996, 271, 1563) by examination of 12 new sites and by quantization of the transferring proton's nuclear motion. Fourteen initial adsorption sites for the HCl are selected via arguments based on HCl incorporation mechanisms for a dynamic ice surface, for the basal-plane and prism face surfaces of ice. Acid ionization at 190 K in those sites is examined via combined electronic structure and classical molecular dynamics methodologies to estimate the reaction Gibbs energies and barriers. In each case examined, the acid ionization step of proton transfer from the HCl to a neighboring water molecule is estimated to be thermodynamically feasible and kinetically rapid.

References

1. B. J. Gertner and J. T. Hynes, Science, 1996, 271, 1563.
2. K. Ando and J. T. Hynes, in Structure and Reactivity in Aqueous Solution: Characterization of Chemical and Biological Systems, ed. C. J. Cramer and D. G. Truhlar, American Chemical Society, Washington, DC, 1994, p. 143; K. Ando and J. T. Hynes, J. Mol. Liq., 1995, 64, 25.
3. K. Ando and J. T. Hynes, J. Phys. Chem., 1997, 101, 10464.
4. S. Solomon, R. R. Garcia, F. S. Rowland and D. J. Wuebbles, Nature (London), 1986, 321, 755.
5. P. J. Crutzen and F. Arnold, Nature (London), 1986, 324, 651; M. B. McElroy, R. J. Salawitch and S. C. Wofsy, Geophys. Res. Lett., 1986, 13, 1296; O. B. Toon, P. Hamill, R. P. Turco and J. Pinto, Geophys. Res. Lett., 1986, 13, 1284; S. Solomon, Rev. Geophys., 1988, 26, 131; R. P. Turco, O. B. Toon and P. Hamill, J. Geophys. Res., 1989, 94, 16493; S. Solomon, Nature (London), 1990, 347, 347.
6. M. J. Molina and F. S. Rowland, Nature (London), 1974, 249, 810; R. J. Cicerone, Science, 1987, 237, 35; M. B. McElroy, R. J. Salawitch and S. C. Wofsy, Planet. Space Sci., 1988, 36, 73; G. S. Henderson, W. F. Evans and J. C. McConnell, J. Geophys. Res., 1990, 95, 1899; World Meteorological Organization (WMO), Scientific Assessment of Stratospheric Ozone 1989, Global Ozone Research and Monitoring Project, Geneva, 1990, Report No. 20; R. P. Wayne, Chemistry of Atmospheres, Oxford University Press, New York, 2nd edn., 1991; P. O. Wennberg, R. C. Cohen, R. M. Stimpfle, J. P. Koplow, J. G. Anderson, R. J. Salawitch, D. W. Fahey, E. L. Woodbridge, E. R. Keim, R. S. Gao, C. R. Webster, R. D. May, D. W. Toohey, L. M. Avallone, M. H. Proffitt, M. Loewenstein, J. R. Podolske, K. R. Chan and S. C. Wofsy, Science, 1994, 266, 398.
7. L. T. Molina and M. J. Molina, J. Phys. Chem., 1987, 91, 433.
8. M. J. Molina, T. L. Tso, L. T. Molina and F. C. Wang, Science, 1987, 238, 1253.
9. M. A. Tolbert, M. J. Rossi, R. Malhotra and D. M. Golden, Science, 1987, 238, 1258; M.-T. Leu, Geophys. Res. Lett., 1988, 15, 17; D. R. Hanson and A. R. Ravishankara, J. Geophys. Res., 1991, 96, 5081; J. P. Abbatt and M. J. Molina, J. Phys. Chem., 1992, 96, 7674; L. T. Chu, M.-T. Leu and L. F. Keyser, J. Phys. Chem., 1993, 97, 12798; J. R. Sodeau, A. B. Horn, S. F. Banham and T. G. Koch, J. Phys. Chem., 1995, 99, 6258; S. F. Banham, A. B. Horn, T. G. Koch and J. R. Sodeau, Faraday Discuss., 1995, 100, 321.
10. D. R. Hanson and A. R. Ravishankara, J. Phys. Chem., 1992, 96, 2682.
11. D. R. Hanson, J. Phys. Chem., 1995, 99, 13059.
12. D. R. Worsnop, C. E. Kolb, M. S. Zaniser, P. Davidovits, L. F. Keyser, M.-T. Leu, M. J. Molina, D. R. Hanson, A. R. Ravishankara, L. R. Williams and M. A. Tolbert, in Progress and Problems in Atmospheric Chemistry, ed. J. R. Barker, World Scientific, Singapore, 1995, vol. 3 of Adv. Ser. Phys. Chem., ch. 18; M. J. Molina, L. T. Molina and D. M. Golden, J. Phys. Chem., 1996, 100, 12888.
13. J. P. Abbatt, K. D. Beyer, A. F. Fucaloro, J. R. McMahon, P. J. Woolridge, R. Zhang and M. J. Molina, J. Geophys. Res., 1992, 97, 15819.
14. A. B. Horn, M. A. Chesters, M. R. S. McCoustra and J. R. Sodeau, J. Chem. Soc., Faraday Trans., 1992, 88, 1077.
15. L. T. Chu, M.-T. Leu and L. F. Keyser, J. Phys. Chem., 1993, 97, 7779.
16. S. C. Wofsy, M. J. Molina, R. J. Salawitch, L. E. Fox and M. B. McElroy, J. Geophys. Res., 1988, 93, 2442; B. G. Koehler, A. M. Middlebrook, L. S. McNeill and M. A. Tolbert, J. Geophys. Res. D, 1993, 98, 10563.
17. J. P. D. Abbatt, K. D. Beyer, A. F. Fucaloro, J. R. McMahan, P. J. Woolridge, R. Zhang and M. J. Molina, J. Geophys. Res., 1992, 97, 15819.
18. D. R. Haynes, N. J. Tro and S. M. George, J. Phys. Chem., 1992, 96, 8502.
19. S. C. Colbeck, J. Cryst. Growth, 1985, 72, 726.
20. G.-J. Kroes and D. C. Clary, Geophys. Res. Lett., 1992, 19, 1355; G.-J. Kroes and D. C. Clary, J. Phys. Chem., 1992, 96, 7079.
21. R. Bianco, B. J. Gertner and J. T. Hynes, Ber. Bunsen-Ges. Phys. Chem., 1998, 102, 518.
22. S. H. Robertson and D. C. Clary, Faraday Discuss., 1995, 100, 309.
23. D. A. Estrin, J. Kohanoff, D. H. Laria and R. O. Weht, Chem. Phys. Lett., 1997, 280, 280.
24. R. N. Pribble and T. S. Zwier, Science, 1994, 265, 75.
25. L. Wang and D. C. Clary, J. Chem. Phys., 1996, 104, 5663.
26. J. D. Graham and J. T. Roberts, J. Phys. Chem., 1994, 98, 5974.
27. B. J. Gertner and J. T. Hynes, unpublished work.
28. J. P. Devlin and V. Buch, J. Phys. Chem., 1995, 99, 16534 and references therein.
29. G. Torchet, P. Schwartz, J. Farges, M. F. de Feraudy and B. Raoult, J. Chem. Phys., 1983, 79, 6196.
30. J. D. Bernal and R. H. Fowler, J. Chem. Phys., 1933, 1, 515.
31. M. J. Packer and D. C. Clary, J. Phys. Chem., 1995, 99, 14323.
32. M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids, Clarendon Press, London, 1987.
33. D. J. Evans, Mol. Phys., 1977, 34, 317; D. J. Evans and S. Murad, Mol. Phys., 1977, 34, 327.
34. W. L. Jorgensen, J. Chandrasekhar, J. D. Madura, R. W. Impey and M. L. Klein, J. Chem. Phys., 1983, 79, 926.
35. J. S. Binkley, J. A. Pople and W. J. Hehre, J. Am. Chem. Soc., 1980, 102, 939; M. S. Gordon, J. S. Binkley, J. A. Pople, W. J. Pietro and W. J. Hehre, J. Am. Chem. Soc., 1982, 104, 2997; W. J. Pietro, M. M. Francl, W. J. Hehre, D. J. DeFrees, J. A. Pople and J. S. Binkley, J. Am. Chem. Soc., 1982, 104, 5039.
36. C. Møller and M. S. Plesset, Phys. Rev., 1934, 46, 618.
37. R. Ditchfield, W. J. Hehre and J. A. Pople, J. Chem. Phys., 1971, 54, 724; W. J. Hehre, R. Ditchfield and J. A. Pople, J. Chem. Phys., 1972, 56, 2257; P. C. Hariharan and J. A. Pople, Theor. Chim. Acta, 1973, 28, 213; M. M. Francl, W. J. Pietro, W. J. Hehre, J. S. Binkley, M. S. Gordon, D. J. DeFrees and J. A. Pople, J. Chem. Phys., 1982, 77, 3654; G. W. Spitznagel, Diplomarbeit, Erlangen, 1982; T. Clark, J. Chandrasekhar, G. W. Spitznagel and P. v. R. Schleyer, J. Comput. Chem., 1983, 4, 294.
38. B. J. Gertner and J. T. Hynes, unpublished work.
39. E. L. Pollock and B. J. Alder, Phys. Rev. Lett., 1977, 39, 299; E. L. Pollock and B. J. Alder, Phys. Rev. Lett., 1978, 41, 903; B. Saager, J. Fischer and M. Neumann, Mol. Simul., 1991, 6, 27.
40. Y. Rhee, J. W. Halley, J. Hautman and A. Rahman, Phys. Rev. B, 1989, 40, 36; J. Hautman and M. L. Klein, Mol. Phys., 1992, 75, 379.
41. A. Warshel and R. M. Weiss, J. Phys. Chem., 1980, 102, 6218; A. Warshel and S. Russel, J. Am. Chem. Soc., 1986, 108, 6569.
42. M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. J. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis and J. A. Montgomery, J. Comput. Chem., 1993, 14, 1347.
43. M. Tachiya, J. Phys. Chem., 1989, 93, 7050.
44. C. H. Bennett, J. Comput. Phys., 1976, 22, 245.
45. W. J. Hehre, R. F. Stewart and J. A. Pople, J. Chem. Phys., 1969, 51, 2657; W. J. Hehre, R. Ditchfield, R. F. Stewart and J. A. Pople, J. Chem. Phys., 1970, 52, 2769; M. S. Gordon, M. D. Bjorke, F. J. Marsh and M. S. Korth, J. Am. Chem. Soc., 1978, 100, 2670.
46. B. R. Johnson, J. Chem. Phys., 1977, 67, 4086.
47. E. E. Nitikin, Theory of Elementary Atomic and Molecular Processes in Gases, Clarendon, Oxford, 1974.
48. See, for example, J. N. Onuchic and P. G. Wolynes, J. Phys. Chem., 1988, 92, 6495 and references therein.
49. M. D. Newton, J. Chem. Phys., 1977, 67, 5535.
50. R. Bianco and J. T. Hynes, J. Phys. Chem. A, 1998, 102, 309.
51. M. Tuckerman, K. Laasonen, M. Sprik and M. Parrinello, J. Phys. Chem., 1995, 99, 5749; M. Tuckerman, K. Laasonen, M. Sprik and M. Parrinello, J. Chem. Phys., 1995, 103, 150; N. Agmon, J. Phys. Chem., 1998, 102, 192 and references therein.