Decay of high Rydberg states: A paradigm for intramolecular dynamics in a congested bound level structure coupled to a continuum

Journal of Chemical Physics

Volumn 104, Issue 4, 1996, Pages 1399-1414

  Remacle, F ^a,c   Levine, R D ^b  

^a UNIVERSITY OF LIÈGE   (Belgium)

^b HEBREW UNIVERSITY OF JERUSALEM   (Israel)

^c FNRS   (Belgium)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0013613319     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.470907     Document Type: Article

References (104)

1. F. F. Crim, Annu. Rev. Phys. Chem. 44, 397 (1993).
2. K. K. Lehmann, G. Scoles, and B. H. Pate, Annu. Rev. Phys. Chem. 45, 241 (1994).
3. Mode Selective Chemistry, edited by J. Jortner, R. D. Levine, and B. Pullman (Kluwer, Dordrecht, 1991).
4. W. L. Hase, in Dynamics of Molecular Collisions, Part B, edited by W. H. Miller (Plenum, New York, 1976), p. 121.
5. F. Remade, J. C. Lorquet, and R. D. Levine, Chem. Phys. Lett. 209, 315 (1993).
6. J. Jortner and R. D. Levine, Adv. Chem. Phys. 47, 1 (1981).
7. F. Remade and R. D. Levine, Phys. Lett. A 173, 284 (1993).
8. R. D. Levine, Quantum Mechanics of Molecular Rate Processes (Clarendon, Oxford, 1969).
9. S. Nordholm and S. A. Rice, J. Chem. Phys. 62, 157 (1975).
10. G. Reiser, W. Habenicht, K. Muller-Dethlefs, and E. W. Schlag, Chem. Phys. Lett. 152, 119 (1988).
11. D. Bahatt, U. Even, and R. D. Levine, J. Chem. Phys. 98, 1744 (1993).
12. X. Zhang, J. M. Smith, and J. L. Knee, J. Chem. Phys. 99, 3133 (1993).
13. W. A. Chupka, J. Chem. Phys. 98, 4520 (1993).
14. E. W. Schlag, W. B. Peatman, and K. Müller-Dethlefs, J. Electron. Spectrosc. 66, 139 (1993).
15. I. Fischer, R. Lindner, and K. Müller-Dethlefs, J. Chem. Soc. Faraday Trans. 90, 2425 (1994);
16. H.-J. Dietrich, R. Linder, and K. Müller-Dethlefs, J. Chem. Phys. 101, 3399 (1994).
17. S. T. Pratt, J. Chem. Phys. 98, 9241 (1993).
18. F. Merkt, J. Chem. Phys. 100, 2623 (1994).
19. M. J. J. Vrakking and Y. T. Lee, Phys. Rev. A 51, R894 (1995).
20. C. E. Alt, W. G. Scherzer, H. L. Selzle, and E. W. Schlag, Chem. Phys. Lett. 224, 366 (1994).
21. F. Merkt and R. N. Zare, J. Chem. Phys. 101, 3495 (1994).
22. M. Bixon and J. Jortner, J. Phys. Chem. 99, 7466 (1995).
23. W. E. Enrst, T. P. Softley, and R. N. Zare, Phys. Rev. A 37, 4172 (1988).
24. M. J. J. Vrakking and Y. T. Lee, J. Chem. Phys. 102, 5566 (1995).
25. A. Mühlpford and U. Even, J. Chem. Phys. (to be published).
26. E. Rabani, L. Ya. Baranov, R. D. Levine, and U. Even, Chem. Phys. Lett. 221, 473 (1994).
27. E. Rabani, R. D. Levine, A. Mühlpford, and U. Even, J. Chem. Phys. 102, 1619 (1995).
28. A. Mühlpford, U. Even, E. Rabani, and R. D. Levine, Phys. Rev. A 51, 3922 (1995).
29. E. Rabani, R. D. Levine, and U. Even, J. Phys. Chem. 98, 8834 (1994).
30. E. W. Schlag and R. D. Levine, J. Phys. Chem. 96, 10 668 (1992).
31. K. Müller-Dethlefs and E. W. Schlag, Annu. Rev. Phys. Chem. 42, 109 (1991).
32. W. G. Sherzer, H. L. Selzle, E. W. Schlag, and R. D. Levine, Phys. Rev. Lett. 72, 1435 (1994).
33. H. Krause and H. J. Neusser, J. Chem. Phys. 99, 6278 (1993).
34. R. Linder, H.-J. Dietrich, and K. Müller-Dethlefs, Chem. Phys. Lett. 228, 417 (1994).
35. F. Merkt and T. P. Softley, Int. Rev. Phys. Chem. 12, 205 (1993).
36. T. F. Gallagher, Rydberg Atoms (Cambridge University, Cambridge, 1994).
37. C. E. Alt, W. G. Scherzer, H. L. Selzle, E. W. Schlag, L. Ya. Baranov, and R. D. Levine, J. Phys. Chem. 99, 1660 (1995).
38. A. ten Wolde, L. D. Noordam, A. Lagendijk, and H. V. van Linden van den Heuvel, Phys. Rev. A 40,485 (1989);
39. M. Nauenberg, C. Stroud, and J. Yeazell, Sci. Am. June 1994, p. 24.
40. O. K. Rice and H. C. Rampsperger, J. Am. Soc. 49, 1617 (1927);
41. L. S. Kassel, J. Phys. Chem. 32, 225 (1928);
42. F. A. Lindeman, Trans. Faraday Soc. 17, 598 (1922).
43. Dynamics of Molecules and Chemical Reactions, edited by R. E. Wyatt and J. Z. H. Zhang (Marcel Dekker, New York, 1996).
44. R. S. Berry, J. Chem. Phys. 45, 1228 (1966).
45. J. N. Bardsley, Chem. Phys. Lett. 1, 229 (1967).
46. A. Russek, M. R. Patterson, and R. L. Becker, Phys. Rev. 167, 17 (1968);
47. B. Ritchie, Phys. Rev. A 6, 1761 (1972).
48. E. E. Eyler and F. M. Pipkin, Phys. Rev. A 27, 2462 (1983);
49. E. E. Eyler, ibid. 34, 2881 (1986).
50. R. D. Gilbert and M. S. Child, Chem. Phys. Lett. 287, 153 (1991).
51. K. Wang, J. A. Stephens, and V. McKoy, J. Phys. Chem. 97, 9874 (1993).
52. H. Nakamura, Int. Rev. Phys. Chem. 10, 123 (1991).
53. F. Remacle, M. Desouter-Lecomte, and J. C. Lorquet, J. Chem. Phys. 91, 4155 (1989).
54. F. Remacle, M. Munster, V. B. Pavlov-Verevkin, and M. DesouterLecomte, Phys. Lett. A 145, 265 (1990).
55. F. Remacle and R. D. Levine, J. Phys. Chem. 95, 7124 (1991).
56. U. Even, M. Ben-Nun, and R. D. Levine, Chem. Phys. Lett. 210, 416 (1993).
57. E. W. Schlag, H. L. Selzle, C. E. Alt, and R. D. Levine (unpublished).
58. L. D. Landau and E. M. Lifshitz, Mechanics, 3rd ed. (Pergamon, Oxford, 1976).
59. L. Ya. Baranov, R. Kris, R. D. Levine, and U. Even, J. Chem. Phys. 100, 186 (1994).
60. U. Peskin, H. Reisler, and W. H. Miller, J. Chem. Phys. 101, 9672 (1994).
61. F. Remacle and R. D. Levine, J. Chin. Chem. Soc. 42, 381 (1995).
62. K. Someda, H. Nakamura, and F. H. Mies, Chem. Phys. 197, 195 (1994).
63. The off-diagonal character of the rate matrix is a general aspect (Refs. 8,9) not in any way unique to the problem of Rydberg states. In pictorial terms, the off-diagonal character is the process known as healing [G. G. Hall and R. D. Levine, J. Chem. Phys. 44, 1567 (1966)], where a state dissociates into the continuum but returns back to be a (different) bound state. Note
64. that this process does enhance the rate of state mixing in the bound subspace (Ref. 49). The only limit that we know of where the rate matrix is guaranteed to be diagonal in a zero order basis, is when there is only one initial state as in the early theory of radiationless transitions, M. Bixon and J. Jortner, J. Chem. Phys. 48, 715 (1968).
65. M. Quack and J. Troe, Ber. Bunsenges. Phys. Chem. 78, 240 (1974).
66. W. L. Hase, Acc. Chem. Res. 16, 258 (1983).
67. W. H. Wong and R. A. Marcus, J. Chem. Phys. 55, 5625 (1971).
68. W. H. Miller, J. Phys. Chem. 92, 22 (1988).
69. F. Remade, M. Desouter-Lecomte, and J. C. Lorquet, Chem. Phys. 153, 201 (1991).
70. The effective Hamiltonian is not Hermitian and so the matrix that diagonalizes it is not unitary. H is however symmetric and so can be diagonalized by a biorthogonal transformation [P. M. Morse and H. Feschbach, Methods of Theoretical Physics (McGraw-Hill, New York, 1953), p. 878].
71. n,n′ (Ref. 8).
72. The dilution effect has been extensively discussed in the literature of radiationless transitions. A review of that work is given in Ref. 6. Earlier reviews include K. F. Freed, Topics Current Chem. 31, 105 (1972)
73. and J. Jortner and S. Mukamel in MTP Series, I. Theor. Chem. (1976).
74. For more recent work see B. Carmeli, I. Scheck, A. Nitzan, and J. Jortner, J. Chem. Phys. 72, 1928 (1980).
75. For a time dependent view of the dilution effect for Rydberg states ("the time stretch") see Ref. 25. Additional references are Ref. 21 and J. Jortner and M. Bixon, J. Chem. Phys. 102, 5636 (1995).
76. K. Müller-Dethlefs, H.-J. Dietrich, and L. Baranov, Phys. Rev. Lett. (in press).
77. C. Bordas, P. F. Brevet, M. Broyer, J. Chevaleyre, P. Labastie, and J. P. Petto, Phys. Rev. Lett. 60, 917 (1988).
78. C. R. Mahon, G. R. Janik, and T. F. Gallagher, Phys. Rev. A 41, 3746 (1990);
79. C. Bordas, P. Brevet, M. Broyer, I. Chevaleyre, and P. Labastie, Europhys. Lett. 3, 789 (1987).
80. D. Farrelly, T. Uzer, P. E. Raines, J. P. Skelton, and J. A. Milligan, Phys. Rev. A 45, 543 (1992).
81. U. Even, R. D. Levine, and R. Berson, J. Phys. Chem. 98, 3472 (1994).
82. The Tel Aviv experiments indicate that roughly 10% of the molecules survive beyond 1 μs. This fraction is observed (Ref. 27) to be much higher if an external magnetic field is imposed, in a direction perpendicular to the external dc field.
83. W. Gordon, Ann. Phys. 2, 1031 (1929).
84. H. A. Bethe and E. E. Salpeter, Quantum Mechanics of One- and Two-Electrons Atoms (Springer, Berlin, 1957).
85. M. L. Zimmerman, M. G. Littman, M. M. Kash, and D. Kleppner, Phys. Rev. A 20, 2251 (1979).
86. S. A. Bhatti, C. L. Cromer, and W. E. Cooke, Phys. Rev. 24, 161 (1981).
87. V. A. Davydkin, V. D. Ovsyannikov, and B. A. Zon, Laser Phys. 3, 449 (1993);
88. D. L. Dorofeyev and B. A. Zon, Phys. Scr. 49, 553 (1994).
89. L. C. Biedenharn, J. M. Blatt, and M. E. Rose, Rev. Mod. Phys. 24, 249 (1952).
90. A. M. Arthurs and A. Dalgarno, Proc. R. Soc. A 256, 540 (1960).
91. D. A. Harmin, Phys. Rev. A 24, 2491 (1981).
92. W. A. Chupka, J. Chem. Phys. 99, 9241 (1993).
93. U. Fano, J. Opt. Soc. Am. 65, 979 (1975).
94. Recent reviews of the quantum defect are C. H. Greene and Ch. Jungen, Adv. At. Mol. Phys. 21, 51 (1985), and Ref. 46.
95. A recent application which emphasizes "final state interactions" is T. P. Softley and A. J. Hudson, J. Chem. Phys. 101, 923 (1994).
96. L. Ya Baranov and R. D. Levine (unpublished).
97. Y. S. Li, R. W. Whitnell, K. R. Wilson, and R. D. Levine, J. Phys. Chem. 97, 3647 (1993).
98. For an example of unimolecular dissociation, see M. Berlinger and Ch. Schlier, J. Chem. Phys. 101, 4750 (1994).
99. It is also of interest to try to identify such regions by stability analysis. See, for example, E. Lee, D. Farrelly, and T. Uzer, Chem. Phys. Lett. 231, 241 (1994).
100. In the unimolecular case, see S. A. Rice and P. Gaspard, Is. J. Chem. 30, 23 (1990), and references therein.
101. A. Henriet, F. Masnou-Seeuws, and O. Dulieu, Z. Phys. D 18, 287 (1991).
102. E. W. Schlag and R. D. Levine, Chem. Phys. Lett. 163, 523 (1989).
103. J. A. Beswick and J. Jortner, Adv. Chem. Phys. 47, 363 (1981).
104. R. D. Levine and J. Jortner, Mode Selective Chemistry, in Ref. 3.