A classical-path surface-hopping study of Mu, H and T hot-atom collisions with F₂

Abstract

The collision dynamics of processes pertinent to the hot-atom chemistry of the hydrogen isotopes Mu, H and T with F₂ are explored using mixed quantum–classical techniques. We use classical-path surface-hopping and pure classical-path multi-surface trajectory methods with a set of 14 coupled potential energy surfaces (PESs) from a diatomics-in-molecules (DIM) model. We compare with results from the standard quasiclassical trajectory (QCT) method applied to the electronic ground state surface of the same DIM model. We compute reaction- and dissociation cross sections for centre-of-mass collision energies ranging from threshold to 20 eV. In order to quantify the notion of electronic non-adiabaticity we introduce various cross sections measuring electronically non-adiabatic processes. We find that non-adiabatic effects give rise to pronounced changes in the dynamics of the Mu+F₂ system. In particular, collision-induced dissociation of F₂ by Mu is an essentially electronically non-adiabatic process, proceeding efficiently by a mechanism involving transitions to excited repulsive PESs. In contrast, QCT calculations on the electronic ground state surface predict vanishingly small Mu+F₂ dissociation cross sections. We also discuss some consequences of this behaviour for simulations of Mu hot-atom chemistry.

References

1. T. Tominaga and E. Tachikawa, Modern Hot Atom Chemistry and Its Applications, Springer, Berlin, 1981.
2. Hot Atom Chemistry: Recent Trends and Applications in the Physical and Life Sciences and Technology, ed. T. Matsuura, Elsevier, Amsterdam, 1984.
3. Handbook of Hot Atom Chemistry, ed. J.-P. Adloff, P. P. Gaspar, M. Imamura, A. G. Maddock, T. Matsuura, H. Sano and K. Yoshihara, Kodansha, Tokyo, 1992.
4. D. C. Walker, Muon and Muonium Chemistry, Cambridge University Press, Cambridge, UK, 1983.
5. D. G. Fleming, M. Senba, D. J. Arseneau, I. D. Reid and D. M. Garner, Can. J. Chem., 1986, 64, 5.
6. D. G. Fleming, Radiat. Phys. Chem., 1986, 28, 115.
7. J. R. Kempton, D. J. Arseneau, D. G. Fleming, M. Senba, A. C. Gonzalez, J. J. Pan, A. Tempelmann and D. M. Garner, J. Phys. Chem., 1991, 95, 7338.
8. M. Senba, D. J. Arseneau and D. G. Fleming, in ref. 3, p. 232.
9. D. J. Malcolme-Lawes, in ref. 2, p. 39.
10. T. Valencich, in ref. 3, p. 188.
11. M. Senba, D. G. Fleming, D. J. Arseneau and H. R. Mayne, personal communication.
12. P. J. Kuntz, in Modern Theoretical Chemistry, Vol. 2: Dynamics of Molecular Collisions, Part B, ed. W. H. Miller, Plenum, New York, 1976, p. 53.
13. Z. B. Alfassi and M. Baer, Chem. Phys., 1981, 63, 275.
14. E. A. Gislason and M. Sizun, Chem. Phys., 1989, 133, 237.
15. E. E. Nikitin, Theory of Elementary Atomic and Molecular Processes in Gases, translated from the Russian by M. J. Kearsley, Clarendon, Oxford, 1974.
16. J. C. Tully, Faraday Discuss., 1998, 110, 407.
17. J. C. Tully, in Modern Methods for Multidimensional Dynamics Computations in Chemistry, ed. D. L. Thompson, World Scientific, Singapore, 1998, p. 34.
18. G. D. Billing, Int. Rev. Phys. Chem., 1994, 13, 309.
19. D. M. Garner, D. G. Fleming and J. H. Brewer, Chem. Phys. Lett., 1978, 55, 163.
20. A. C. Gonzalez, I. D. Reid, D. M. Garner, M. Senba, D. G. Fleming, D. J. Arseneau and J. R. Kempton, J. Chem. Phys., 1989, 91, 6164.
21. D. G. Fleming and M. Senba, in Perspectives of Meson Science, ed. T. Yamazaki, K. Nakai and K. Nagamine, Elsevier, Amsterdam, 1992, p. 219.
22. K. H. Homann, H. Schweinfurth and J. Warnatz, Ber. Bunsen-Ges. Phys. Chem., 1977, 81, 724.
23. N. Jonathan, S. Okuda and D. Timlin, Mol. Phys., 1972, 24, 1143; erratum, ibid., 1973, 85, 496.
24. J. C. Polanyi, J. J. Sloan and J. Wanner, Chem. Phys., 1976, 13, 1.
25. L. S. Dzelzkalns and F. Kaufman, J. Chem. Phys., 1982, 77, 3508.
26. J. N. L. Connor, A. Laganà, A. F. Turfa and J. C. Whitehead, J. Chem. Phys., 1981, 75, 3301.
27. R. Steckler, D. G. Truhlar and B. C. Garrett, Int. J. Quantum Chem. Symp., 1986, 20, 495.
28. B. C. Garrett, R. Steckler and D. G. Truhlar, Hyperfine Interact., 1986, 32, 779.
29. D. C. Clary and J. N. L. Connor, J. Chem. Phys., 1981, 75, 3329.
30. F. O. Ellison, J. Am. Chem. Soc., 1963, 85, 3540.
31. P. J. Kuntz, in Theoretical Models of Chemical Bonding, Part 2: The Concept of the Chemical Bond, ed. Z. B. Maksić, Springer, Berlin, 1990, p. 321.
32. W. Jakubetz and P. J. Kuntz, Chem. Phys., 1994, 179, 241.
33. D. G. Truhlar and C. J. Horowitz, J. Chem. Phys., 1978, 68, 2466; erratum, ibid., 1979, 71, 1514.
34. A. J. C. Varandas, F. B. Brown, C. A. Mead, D. G. Truhlar and N. C. Blais, J. Chem. Phys., 1987, 86, 6258.
35. A. I. Boothroyd, W. J. Keogh, P. G. Martin and M. R. Peterson, J. Chem. Phys., 1996, 104, 7139.
36. P. J. Kuntz, J. Chem. Phys., 1991, 95, 141.
37. M. Amarouche, F. X. Gadéa and J. Durup, Chem. Phys., 1989, 130, 145.
38. F. X. Gadéa and M. Amarouche, Chem. Phys., 1990, 140, 385.
39. D. G. Truhlar and J. T. Muckerman, in Atom-Molecule Collision Theory—A Guide for the Experimentalist, ed. R. B. Bernstein, Plenum, New York, 1979, p. 505.
40. W. Jakubetz and P. J. Kuntz, to be published.
41. J. J. Duggan and R. Grice, J. Chem. Phys., 1983, 78, 3842.
42. R. Polák, personal communication.
43. R. Polák, J. Vojtík and F. Schneider, Chem. Phys. Lett., 1982, 85, 107.
44. R. Polák and P. J. Kuntz, Chem. Phys., 1992, 168, 301.
45. G. Herzberg and H. C. Longuet-Higgins, Discuss. Faraday Soc., 1963, 35, 77.
46. G. J. Atchity, S. S. Xantheas and K. Ruedenberg, J. Chem. Phys., 1991, 95, 1862.
47. I. Last and M. Baer, J. Chem. Phys., 1984, 80, 3246.
48. P. B. Benneyworth, G. G. Balint-Kurti, M. J. Davis and I. H. Williams, J. Phys. Chem., 1992, 96, 4346.
49. G. L. Fox and H. B. Schlegel, J. Am. Chem. Soc., 1993, 115, 6870.
50. T. Takayanagi and Y. Kurosaki, J. Phys. Chem. A, 1997, 101, 7098.
51. M. Bittererová, S. Biskupic, H. Lischka and W. Jakubetz, in preparation.
52. P. J. Kuntz, B. I. Niefer and J. J. Sloan, J. Chem. Phys., 1988, 88, 3629.
53. P. J. Kuntz, in Selectivity in Chemical Reactions. Proceedings of the NATO Advanced Research Workshop on Selectivity in Chemical Reactions, Bowness-on-Windermere, UK, 7–11 September 1987, ed. J. C. Whitehead, Kluwer, Dordrecht, 1988, p. 403.
54. G. D. Billing, Chem. Phys., 1975, 9, 359.
55. S. C. Mehrotra and J. E. Boggs, J. Chem. Phys., 1975, 63, 4618.
56. K. J. McCann and M. R. Flannery, J. Chem. Phys., 1975, 63, 4695.
57. D. J. Diestler, J. Chem. Phys., 1983, 78, 2240.
58. L. L. Halcomb and D. J. Diestler, J. Chem. Phys., 1986, 84, 3130.
59. W. H. Miller and C. W. McCurdy, J. Chem. Phys., 1978, 69, 5163.
60. H.-D. Meyer and W. H. Miller, J. Chem. Phys., 1979, 70, 3214.
61. A. Bjerre and E. E. Nikitin, Chem. Phys. Lett., 1967, 1, 179.
62. J. C. Tully and R. K. Preston, J. Chem. Phys., 1971, 55, 562.
63. N. C. Blais and D. G. Truhlar, J. Chem. Phys., 1983, 79, 1334.
64. G. Parlant and E. A. Gislason, J. Chem. Phys., 1989, 91, 4416.
65. J. C. Tully, J. Chem. Phys., 1990, 93, 1061.
66. M. F. Herman, J. Chem. Phys., 1984, 81, 754.
67. J. C. Tully, J. Chem. Phys., 1974, 60, 3042.
68. J. Durup, Chem. Phys. Lett., 1986, 132, 299.
69. S. Hammes-Schiffer and J. C. Tully, J. Chem. Phys., 1994, 101, 4657.
70. R. Wolfgang, Prog. React. Kinet., 1965, 3, 97.
71. B. A. Hodgson and J. C. Polanyi, J. Chem. Phys., 1971, 55, 4745.
72. J. N. L. Connor and A. Laganà, Mol. Phys., 1979, 38, 657.
73. N. C. Blais, D. G. Truhlar and C. A. Mead, J. Chem. Phys., 1988, 89, 6204.
74. A. I. Voronin, J. M. C. Marques and A. J. C. Varandas, J. Phys. Chem. A, 1998, 102, 6057.
75. C. W. Eaker and G. C. Schatz, J. Chem. Phys., 1988, 89, 6713.
76. L. D. Landau, Phys. Z. Sowjetunion, 1932, 2, 46; reprinted in Collected Papers of L. D. Landau, ed. and with an introduction by D. Ter Haar, Pergamon, Oxford, 1965, p. 63.
77. C. Zener, Proc. R. Soc. London, Ser. A, 1932, 137, 696.
78. H. S. W. Massey, Rep. Prog. Phys., 1949, 12, 248.