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Infrared multiphoton excitation dynamics of CF3I. II. Collisional effects on vibrational and rotational state populations
Time-resolved resonantly enhanced multiphoton ionization spectroscopy of I(2P3/2) and I(2P1/2) dissociation products of CF3I can be used to characterize populations of highly-excited CF3I*. This techn...
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Canonical variational transition state theory for dissipative systems: Application to generalized Langevin equations

J. Chem. Phys. 96, 8877 (1992); doi:10.1063/1.462245

Issue Date: 15 June 1992

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Anatoli Frishman and Eli Pollak
Chemical Physics Department, Weizmann Institute of Science, Rehovot, 76100, Israel
A numerical solution for the canonical variational dividing surface of two degree of freedom conservative systems is presented. The method is applied to reaction rates in dissipative systems whose dynamics is described by a generalized Langevin equation. Applications include a cubic and a quartic well using Ohmic and memory friction. For Ohmic friction, we find that in almost all cases, curvature of the optimal dividing surface may be neglected and the Kramers spatial diffusion limit for the rate is in practice an upper bound. For a Gaussian memory friction and a cubic oscillator, we compare the present theory with numerical simulations and other approximate theories presented by Tucker et al. [J. Chem. Phys. 95, 5809 (1991)]. For the quartic oscillator and exponential friction, we discover a strong suppression of the transmission coefficient and the reaction rate whenever the reduced static friction is of the same order of the reduced memory time. We also show that in this case, there is a strong suppression of the energy diffusion process in the reactants' well. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 3 January 1992; accepted 2 March 1992
Permalink: http://link.aip.org/link/?JCPSA6/96/8877/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.20.Db
    Physical chemistry Chemical kinetics Statistical theories (including transition state)
  • 02.70.+d
    Mathematical methods in physics Computational techniques
  • YEAR: 1992

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
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REFERENCES (25)
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  1. P. Pechukas, in Dynamics of Molecular Collisions, Part B, edited by W. H. Miller (Plenum, New York, 1976), p. 269.
  2. P. Pechukas, Annu. Rev. Phys. Chem. 32, 159 (1981).
  3. E. P. Wigner, Trans. Faraday Soc. 34, 29 (1938),
  4. J. C. Keck, Adv. Chem. Phys. 13, 85 (1967).
  5. E. Pollak, in Theory of Chemical Reaction Dynamics, edited by M. Baer (CRC, Boca Raton, FL, 1985), Vol. 3, p. 123.
  6. W. H. Miller, J. Chem. Phys. 61, 1823 (1974).
  7. B. C. Garrett and D. G. Truhlar, J. Chem. Phys. 76, 1853 (1982).
  8. E. Pollak, J. Phys. Chem. 95, 10235 (1991).
  9. S. C. Tucker and E. Pollak, J. Stat. Phys. 66, 975 (1992).
  10. S. C. Tucker, M. E. Tuckerman, B. J. Berne, and E. Pollak, J. Chem. Phys. 95, 5809 (1991).
  11. E. Pollak, Mod. Phys. Lett. B 5, 13 (1991).
  12. E. Pollak, S. C. Tucker, and B. J. Berne, Phys. Rev. Lett. 65, 1399 (1990).
  13. E. Pollak, J. Chem. Phys. 93, 1116 (1990).
  14. E. Pollak, J. Chem. Phys. 95, 533 (1991).
  15. H. A. Kramers, Physica 7, 284 (1940).
  16. R. F. Grote and J. T. Hynes, J. Chem. Phys. 73, 2715 (1980).
  17. For some history on this problem, see L. D. Landau and E. M. Lifshitz, Mechanics, 3rd ed. (Pergamon, Oxford, 1976), Chap. 44.
  18. R. Zwanzig, J. Stat. Phys. 9, 215 (1973).
  19. A. O. Caldeira and A. J. Leggett, Phys. Rev. Lett. 46, 211 (1981);
    20. Ann. Phys. (NY) 149, 374 (1983).
  20. E. Pollak, J. Chem. Phys. 85, 865 (1986);
    21. A. M. Levine, M. Shapiro, and E. Pollak, ibid. 88, 1959 (1988).
  21. E. Pollak, H. Grabert, and P. Hänggi, J. Chem. Phys. 91, 4073 (1989).
  22. N. De Leon and B. J. Berne, J. Chem. Phys. 77, 283 (1982).
  23. K. Stefanski and E. Pollak, Chem. Phys. 134, 37 (1989).
  24. J. B. Straus and G. A. Voth, J. Chem. Phys. (in press).
  25. W. H. Miller, S. D. Schwartz, and J. Tromp, J. Chem. Phys. 79, 4889 (1983).
  26. G. A. Voth, D. Chandler, and W. H. Miller, J. Chem. Phys. 91, 7749 (1989).

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