Rate coefficients for the reaction and relaxation of H2O in specific vibrational states with H atoms and H2O

(Note: The full text of this document is currently only available in the PDF Version )

Peter W. Barnes, Paul Sharkey, Ian R. Sims and Ian W. M. Smith


Abstract

Rate coefficients are reported for the removal of H2O in selected vibrational states in collisions with H atoms. Pulses of tunable infrared radiation have been employed to excite H2O molecules to the specific vibrational levels ∣04〉-, ∣13〉-, ∣03〉-, ∣12〉- and ∣02〉-2〉, where the notation is that used by Sinha etal. (A. Sinha, M. C. Hsaio and F. F. Crim, J.Chem. Phys., 1991, 94, 4928), in the presence of known concentrations of both H atoms and H2O. OH radicals formed either in v=0 or v=1 by the reaction of H atoms with the vibrationally excited H2O are observed by laser-induced fluorescence. Kinetic data are derived from the variation of LIF intensity with delay time between the infrared pump and ultraviolet probe lasers. Rate coefficients are reported for three kinds of process: (i) the removal of excited H2O molecules from the initially excited level by the sum of reaction and relaxation with H atoms, (ii) the relaxation of excited H2O molecules from the initially excited level by collisions with unexcited H2O, and (iii) the relaxation of OH(v=1) by H atoms and H2O. The results are compared with previous experimental data, especially that on selective vibrational enhancement of endothermic chemical reactions, and with the results of theoretical calculations on the H+H2O reaction.


References

  1. S. M. Auerbach and W. H. Miller, J. Chem. Phys., 1994, 100, 1103 CrossRef CAS.
  2. (a) J. F. Castillo, D. E. Manolopoulos, K. Stark and H.-J. Werner, J. Chem. Phys., 1996, 104, 6531 CrossRef CAS; (b) F. J. Aoiz, L. Banares, B. Martinez-Haya, J. F. Castillo, D. E. Manolopoulos, K. Stark and H.-J. Werner, J. Phys. Chem., 1997, 101, 6403 Search PubMed.
  3. For example, (a) R. E. Continetti, B. A. Balko and Y. T. Lee, J. Chem. Phys., 1990, 93, 5719 CrossRef CAS; (b) L. Schmeider, K. Seekamp-Rahn, J. Borkowski, E. Wrede, K. H. Welge, F. J. Aoiz, L. Banares, M. J. D'Mello, V. J. Herrero, V. Saez-Rabanos and R. E. Wyatt, Science, 1995, 269, 207 CrossRef CAS; (c) H. Xu, N. E. Shafer-Ray, F. Merkt, D. J. Hughes, M. Springer, R. P. Tuckett and R. N. Zare, J. Chem. Phys., 1995, 103, 5157 CrossRef CAS.
  4. (a) D. M. Neumark, A. M. Wodtke, G. N. Robinson, C. C. Hayden and Y. T. Lee, J. Chem. Phys., 1985, 82, 3045 CrossRef CAS; (b) D. M. Neumark, A. M. Wodtke, G. N. Robinson, C. C. Hayden, K. Shobatake, R. K. Sparks, T. P. Schafer and Y. T. Lee, J. Chem. Phys., 1985, 82, 3067 CrossRef CAS.
  5. C. B. Moore and I. W. M. Smith, J. Phys. Chem., 1996, 100, 12848 CrossRef CAS.
  6. (a) D. C. Clary, J. Phys. Chem., 1994, 98, 10678 CrossRef CAS; (b) D. C. Clary, Science, 1998, 279, 1879 CrossRef CAS.
  7. (a) K. Kleinermanns and J. Wolfrum, Appl. Phys. B, 1984, 34, 5; (b) A. Jacobs, H. R. Volpp and J. Wolfrum, Chem. Phys. Lett., 1992, 196, 249 CrossRef CAS; (c) K. Kessler and K. Kleinermanns, Chem. Phys. Lett., 1992, 190, 145 CrossRef CAS; (d) A. Jacobs, H. R. Volpp and J. Wolfrum, J. Chem. Phys., 1994, 100, 1936 CrossRef CAS.
  8. (a) M. J. Bronowski, W. R. Simpson and R. N. Zare, J. Chem. Phys., 1991, 95, 8647 CrossRef; (b) M. J. Bronowski, W. R. Simpson and R. N. Zare, J. Phys. Chem., 1993, 97, 2194 CrossRef; (c) M. J. Bronowski, W. R. Simpson and R. N. Zare, J. Phys. Chem., 1993, 97, 2204 CrossRef; (d) D. E. Adelman, S. V. Filseth and R. N. Zare, J. Chem. Phys., 1993, 98, 4636 CrossRef CAS.
  9. (a) A. Sinha, J. Phys. Chem., 1990, 94, 4391 CrossRef CAS; (b) A. Sinha, M. C. Hsiao and F. F. Crim, J. Chem. Phys., 1991, 94, 4928 CrossRef CAS; (c) M. C. Hsiao, A. Sinha and F. F. Crim, J. Phys. Chem., 1991, 95, 8263 CrossRef CAS; (d) A. Sinha, M. C. Hsiao and F. F. Crim, J. Chem. Phys., 1991, 94, 4928 CrossRef CAS; (e) A. Sinha, J. D. Thoemke and F. F. Crim, J. Chem. Phys., 1992, 96, 372 CrossRef CAS; (f) R. B. Metz, J. D. Thoemke, J. M. Pfeiffer and F. F. Crim, J. Chem. Phys., 1993, 99, 1744 CrossRef CAS; (g) J. D. Thoemke, J. M. Pfeiffer, R. B. Metz and F. F. Crim, J. Phys. Chem., 1995, 99, 13748 CrossRef CAS.
  10. G. Hawthorne, P. Sharkey and I. W. M. Smith, J. Chem. Phys., 1998, 108, 4693 CrossRef CAS.
  11. (a) R. B. Metz, J. M. Pfeiffer, J. D. Thoemke and F. F. Crim, Chem. Phys. Lett., 1994, 221, 347 CrossRef CAS; (b) J. M. Pfeiffer, R. B. Metz, J. D. Thoemke, E. Woods and F. F. Crim, J. Chem. Phys., 1996, 104, 4490 CrossRef CAS.
  12. C. Kreher, R. Theini and K.-H. Gericke, J. Chem. Phys., 1996, 104, 4481 CrossRef CAS.
  13. M. Alagia, N. Balucani, P. Casavecchia, D. Stranges and G. G. Volpi, J. Chem. Phys., 1993, 98, 2459 CrossRef CAS.
  14. This notation for the vibrational states of H2O signifies the numbers of vibrational quanta in the two local OH-bond stretching modes in H2O and is explained fully in the Appendix to ref. 9(d).
  15. I. W. M. Smith and R. Zellner, J. Chem. Soc., Farday Trans. 2, 1973, 70, 1045 Search PubMed.
  16. A. R. Ravishankara, J. M. Nicovich, R. L. Thompson and F. P. Tully, J. Phys. Chem., 1981, 85, 2498 CrossRef CAS.
  17. G. C. Light and J. H. Matsumoto, Chem. Phys. Lett., 1978, 58, 578 CrossRef CAS.
  18. R. Zellner, J. Phys. Chem., 1979, 83, 18 CrossRef CAS.
  19. G. P. Glass and B. K. Chaturvedi, J. Chem. Phys., 1981, 75, 2749 CrossRef CAS.
  20. G. P. Glass, H. Endo and B. K. Chaturvedi, J. Chem. Phys., 1982, 77, 5450 CrossRef CAS.
  21. R. A. Brownsword, M. Hillenkamp, P. Schmiechen, H. -R. Volpp and J. Wolfrum, Chem. Phys. Lett., 1997, 275, 325 CrossRef CAS.
  22. (a) G. C. Schatz, M. C. Colton and J. L. Grant, J. Phys. Chem., 1984, 88, 2971 CrossRef CAS; (b) K. Kudla and G. C. Schatz, J. Chem. Phys., 1993, 98, 4644 CrossRef.
  23. (a) K. S. Bradley and G. C. Schatz, J. Chem. Phys., 1994, 98, 3788 CAS; (b) G. Lendvay, K. S. Bradley and G. C. Schatz, J. Chem. Phys., 1999, 110, 2963 CrossRef CAS.
  24. G. C. Schatz, G. Wu, G. Lendvay, D.-C. Fang and L. B. Harding, Faraday Discuss., 1999, 113, 151 RSC.
  25. J. Palma, J. Echave and D. C. Clary, J. Chem. Soc., Faraday Trans., 1997, 93, 841 RSC.
  26. A. D. Isaacson and D. G. Truhlar, J. Chem. Phys., 1982, 76, 1380 CrossRef CAS.
  27. T. N. Truong, J. Chem. Phys., 1989, 90, 977 CrossRef CAS.
  28. (a) D. C. Clary, J. Chem. Phys., 1991, 95, 7298 CrossRef CAS; (b) D. C. Clary, J. Chem. Phys., 1992, 96, 3656 CrossRef CAS; (c) J. Echave and D. C. Clary, J. Chem. Phys., 1994, 100, 401 CrossRef.
  29. D. C. Clary, Chem. Phys. Lett., 1992, 192, 34 CrossRef CAS.
  30. (a) U. Manthe, T. Seideman and W. H. Miller, J. Chem. Phys., 1993, 99, 10078 CrossRef CAS; (b) U. Manthe, T. Seideman and W. H. Miller, J. Chem. Phys., 1994, 101, 4759 CrossRef CAS.
  31. D. Neuhauser, J. Chem. Phys., 1994, 100, 9272 CrossRef CAS.
  32. (a) D. H. Zhang and J. Z. H. Zhang, J. Chem. Phys., 1994, 101, 1146 CrossRef CAS; (b) W. Zhu, J. Dai, J. Z. H. Zhang and D. H. Zhang, J. Chem. Phys., 1996, 105, 4481.
  33. (a) D. H. Zhang and J. C. Light, J. Chem. Phys., 1996, 104, 4544 CrossRef CAS; (b) D. H. Zhang and J. C. Light, J. Chem. Phys., 1996, 105, 1291 CrossRef CAS.
  34. S. K. Pogrebnya, J. Echave and D. C. Clary, J. Chem. Phys., 1997, 107, 8975 CrossRef.
  35. G. C. Schatz and H. Elgersma, Chem. Phys. Lett., 1980, 73, 21 CrossRef CAS.
  36. S. P. Walch and T. H. Dunning, J. Chem. Phys., 1980, 72, 1303 CrossRef CAS.
  37. (a) A. D. Isaacson, J. Phys. Chem., 1992, 96, 531 CrossRef CAS; (b) A. D. Isaacson and S.-C. Hung, J. Chem. Phys., 1994, 101, 3928 CrossRef CAS; (c) A. D. Isaacson, J. Chem. Phys., 1997, 107, 3832 CrossRef CAS.
  38. G. Ochoa de Aspuru and D. C. Clary, J. Phys. Chem., 1998, 102, 9631 Search PubMed.
  39. M. Alagia, N. Balucani, P. Casavecchia, D. Stranges, G. Volpi, D. C. Clary, A. Kliesch and H.-J. Werner, Chem. Phys., 1996, 207, 389 CrossRef CAS.
  40. (a) R. D. Levine and J. Manz, J. Chem. Phys., 1975, 63, 4280 CrossRef CAS; (b) E. Pollak and R. D. Levine, Chem. Phys. Lett., 1976, 39, 199 CrossRef CAS; (c) R. D. Levine, Chem. Phys. Lett., 1976, 39, 205 CrossRef CAS.
  41. I. W. M. Smith, Kinetics and Dynamics of Elementary Gas Reactions, Buterworths, London, 1980 Search PubMed.
  42. (a) A. McKenzie and M. F. R. Mulcahy, J. Chem. Soc., Faraday Trans. 1, 1974, 70, 549 RSC; (b) M. J. Howard, PhD thesis, University of Cambridge, 1981.
  43. L. S. Rothman, C. P. Rinsland, A. Goldman, S. T. Massie, D. P. Edwards, J. M. Flaud, A. Perrin, C. CamyPeyret, V. Dana, J. Y. Mandin, J. Schroeder, A. McCann, R. R. Gamache, R. B. Wattson, K. Yoshino, K. V. Chance, K. W. Jucks, L. R. Brown, V. Nemtchinov and P. Varanasi, J. Quant. Spectrosc. Radiat. Transfer, 1998, 60, 665 CrossRef CAS.
  44. I. W. M. Smith and M. D. Williams, J. Chem. Soc., Faraday Trans. 2, 1985, 81, 1849 RSC.
  45. I. W. M. Smith, Acc. Chem. Res., 1976, 9, 161 CrossRef CAS.
  46. J. Finzi, F. E. Hovis, V. N. Panfilov, P. Hess and C. B. Moore, J. Chem. Phys., 1977, 67, 4053 CrossRef CAS.
  47. P. F. Zittel and D. E. Masturzo, J. Chem. Phys., 1989, 90, 977 CrossRef CAS.
  48. I. W. M. Smith, J. Chem. Soc., Faraday Trans., 1997, 93, 3741 RSC.
  49. M. J. Howard and I. W. M. Smith, J. Chem. Soc., Faraday Trans. 2, 1982, 78, 1043 Search PubMed.
  50. J. J. Margitan, F. Kaufman and J. G. Anderson, Chem. Phys. Lett., 1975, 34, 485 CrossRef CAS.
  51. R. L. Vander Wal, J. L. Scott and F. F. Crim, J. Chem. Phys., 1991, 94, 1859 CrossRef CAS.
  52. J. F. Bott and R. F. Heidner III, J. Chem. Phys., 1977, 66, 2878 CrossRef CAS.
  53. R. Atkinson, D. L. Baulch, R. A. Cox, R. F. Hampson, J. A. Kerr and J. Troe, J. Phys. Chem Ref. Data, 1997, 26, 521 CAS.
  54. B. E. Holmes and D. W. Setser, in Physical Chemistry of Fast Reactions: Vol. 2 Reaction Dynamics, ed. I. W. M. Smith, Plenum Press, New York, 1980, p. 83 Search PubMed.
  55. Estimated using the rate coefficient for the ‘forward’ reaction between OH + H2(see refs. 14, 15 and 52) and the equilibrium constant.
  56. (a) J. C. Polanyi and K. B. Woodall, J. Chem. Phys., 1972, 57, 1574 CrossRef CAS; (b) J. C. Polanyi, Acc. Chem. Res., 1972, 5, 161 CrossRef CAS.
  57. I. W. M. Smith, in Physical Chemistry of Fast Reactions: Vol. 2 Reaction Dynamics, ed. I. W. M. Smith, Plenum Press, New York, 1980, p. 1 Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.