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Volumn 105, Issue 13, 1996, Pages 5446-5454

Solvent dynamics: Modified Rice-Ramsperger-Kassel-Marcus theory. II. Vibrationally assisted case

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EID: 0001271733     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.472385     Document Type: Article
Times cited : (18)

References (72)
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    • edited by H. Hartmann Springer, Berlin
    • R. A. Marcus, in Chemische Elementarprozesse, edited by H. Hartmann (Springer, Berlin, 1968), p. 348;
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    • Marcus, R.A.1
  • 9
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    • (E)
    • J. Chem. Phys. 80, 592 (E) (1984);
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  • 10
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    • J. Chem. Phys. 79, 2042 (1983).
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    • J. Chem. Phys. 95, 3325 (1991);
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    • J. Chem. Phys. 102, 9565 (1995);
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    • A Smoluchowski-type equation for a different process, namely for bimolecular diffusion-controlled reactions with a distributed reaction sink has been given by G. Wilemski and M. Fixman, J. Chem. Phys. 58, 4009 (1973).
    • (1973) J. Chem. Phys. , vol.58 , pp. 4009
    • Wilemski, G.1    Fixman, M.2
  • 40
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    • Physica A 166, 585 (1990);
    • (1990) Physica A , vol.166 , pp. 585
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    • J. Chem. Phys. 93, 1116 (1990);
    • (1990) J. Chem. Phys. , vol.93 , pp. 1116
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    • the best choice for this hypersurface is the one with the fewest recrossings by trajectories. A family of hypersurfaces is defined, hopefully where some member has few or negligible recrossings, and the family serves to define the reaction coordinate Q. In practice, only in the simplest case, namely where the potential energy is a quadratic function of the coordinates in the transition state region, can Q readily be determined, namely as the coordinate associated with the mode of imaginary frequency at the saddle point. However, for more general systems, finding the best Q for reactions involving rapture of bonds and floppy motions has been an impossible task. At most, one seeks the best Q among a limited class of choices of Q as in
    • Classically, the transition state is a hypersurface in the classical phase space and, as Wigner has pointed out [E. Wigner, Trans. Faraday Soc. 34, 29 (1938)] the best choice for this hypersurface is the one with the fewest recrossings by trajectories. A family of hypersurfaces is defined, hopefully where some member has few or negligible recrossings, and the family serves to define the reaction coordinate Q. In practice, only in the simplest case, namely where the potential energy is a quadratic function of the coordinates in the transition state region, can Q readily be determined, namely as the coordinate associated with the mode of imaginary frequency at the saddle point. However, for more general systems, finding the best Q for reactions involving rapture of bonds and floppy motions has been an impossible task. At most, one seeks the best Q among a limited class of choices of Q [as in
    • (1938) Trans. Faraday Soc. , vol.34 , pp. 29
    • Wigner, E.1
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    • J. Phys. Chem. ibid. 89, 4181 (1985);
    • (1985) J. Phys. Chem. , vol.89 , pp. 4181


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