Abinitio calculations of the catalytic impact of H2SO4 and HSO4- on the reaction of HCl with ClNO3

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Peter Beichert and Otto Schrems


Abstract

The reaction of chlorine nitrate with hydrogen chloride catalysed by sulfuric acid molecules and by the hydrogen sulfate anion has been investigated by means of abinitio calculations at Hartree–Fock and MP2 levels of theory. Geometries of reactants, products and transition states have been optimized using 6-31G** and 6-31++G(2D,2P) basis sets. While the reaction barrier of the gas phase reaction does not decrease significantly with sulfuric acid, it vanishes completely if the hydrogen sulfate anion is involved. The reaction occurs in several associative steps which do not have a reaction barrier. Implications of the results for heterogeneous reactions in the stratosphere on sulfuric acid aerosol surfaces or in the bulk are discussed.


References

  1. S. Solomon, R. R. Garcia, F. S. Rowland and D. J. Wuebbles, Nature, 1986, 321, 755 CrossRef CAS.
  2. O. B. Toon and R. P. Turco, Sci. Am., 1991, 264, 68 Search PubMed.
  3. W. H. Brune, J. G. Anderson, D. W. Toohey and D. W. Fahey, Science, 1991, 252, 1260 CAS.
  4. A. R. Ravishankara and D. R. Hanson, J. Geophys. Res., 1996, 101, 3885 CAS.
  5. J. P. Abbatt and M. J. Molina, J. Phys. Chem., 1992, 96, 7674 CrossRef CAS.
  6. L. T. Chu, M. T. Leu and L. F. Keyser, J. Phys. Chem., 1993, 97, 12798 CrossRef CAS.
  7. D. R. Hanson and A. R. Ravishankara, J. Geophys. Res., 1991, 96, 5081 CAS.
  8. D. R. Hanson and A. R. Ravishankara, J. Phys. Chem., 1992, 96, 2682 CrossRef CAS.
  9. M. T. Leu, Geophys. Res. Lett., 1988, 15, 17 CAS.
  10. M. T. Leu, S. B. Moore and L. F. Keyser, J. Phys. Chem., 1991, 95, 7763 CrossRef CAS.
  11. M. J. Molina, T. L. Tso, L. T. Molin and F. C. Y. Wang, Science, 1987, 238, 1252.
  12. M. A. Tolbert, M. J. Rossi, R. Malhotra and D. M. Golden, Science, 1987, 238, 1258 CAS.
  13. B. M. Haas, K. C. Crellin, K. T. Kuwata and M. Okumura, J. Phys. Chem., 1994, 98, 6740 CrossRef CAS.
  14. C. M. Nelson and M. Okumura, J. Phys. Chem., 1992, 96, 6112 CrossRef CAS.
  15. R. Bianco and J. T. Hynes, J. Phys. Chem. A, 1999, 103, 3797 CrossRef CAS.
  16. A. M. Mebel and K. Morokuma, J. Phys. Chem., 1996, 100, 2985 CrossRef CAS.
  17. M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. J. Su, T. L. Windus, H. M. Dupuis and J. A. Montgomery, J. Comput. Chem., 1993, 14, 1347 CrossRef CAS.
  18. P. Beichert and O. Schrems, J. Phys. Chem. A, 1998, 102, 10540 CrossRef CAS.
  19. G. Schaftenaar, “Molden” University of Nijmegen, The Netherlands, 1998; http://www.caos.kun.nl/~schaft/molden/molden.html.
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