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Dynamics of liquid state chemical reactions: Photodissociation dynamics and geminate recombination of molecular iodine in liquid solution
1.C. L. Brooks III, M. W. Balk and S. A. Adelman, J. Chem. Phys. 79, 784 (1983).
2.References 3—16 constitute a representative sample of the experimental and theoretical work incorporating the concept of the cage effect in the study of iodine recombination.
3.C. A. Langhoff, B. Moore, and M. DeMeuse, J. Am. Chem. Soc. 104, 3576 (1982).
4.P. Bado, P. H. Berens, and K. R. Wilson, Proc. Soc. Photo‐Optic Instrum. Engin. 322, (1982).
5.D. F. Kelley and P. M. Rentzepis, Chem. Phys. Lett. 85, 85 (1982).
6.(a) T. J. Chuang, G. W. Hoffman, and K. B. Eisenthal, Chem. Phys. Lett. 25, 201 (1974);
6.(b) C. A. Langhoff, K. Gnadig, and K. B. Eisenthal, Chem. Phys. 46, 117 (1980).
7.(a) J. Frank and E. Rabinowitch, Trans. Faraday Soc. 30, 120 (1934);
7.(b) E. Rabinowitch and W. C. Wood, Trans. Faraday Soc. 32, 1381 (1936)., Trans. Faraday Soc.
8.D. J. Nesbitt and J. T. Hynes, J. Chem. Phys. 77, 2130 (1982).
9.M. Schell, R. Kapral, and R. I. Cukier, J. Chem. Phys. 75, 5879 (1981).
10.J. T. Hynes, R. Kapral, and G. M. Torrie, J. Chem. Phys. 72, 177 (1980).
11.D. L. Bunker and B. S. Jacobson, J. Am. Chem. Soc. 94, 1843 (1972).
12.(a) The basic principles of the molecular timescale generalized Langevin equation (MTGLE) theory are presented in S. A. Adelman, Adv. Chem. Phys. 44, 143 (1980);
12.(b) The mathematical structure of the MTGLE theory is given in S. A. Adelman, J. Chem. Phys. 74, 4646 (1981);
12.(c) The formal framework for application of the MTGLE theory to liquid solution reactions is presented in S. A. Adelman, J. Chem. Phys. 73, 3145 (1980). There are unfortunately a number of misprints in this paper. These are corrected in Refs. 13; , J. Chem. Phys.
12.(d) The MTGLE theory emerged as a generalization of the work of S. A. Adelman and J. D. Doll, J. Chem. Phys. 64, 2375 (1976)
12.on gas‐solid collisions, which was motivated by an important early paper by R. Zwanzig, J. Chem. Phys. 32, 1173 (1960).
13.For a sophisticated application of the MTGLE theory (a) to calculation of reagent configuration dependent correlation functions see C. L. Brooks III and S. A. Adelman, J. Chem. Phys. 76, 1007 (1982);
13.(b) to modeling of reagent configuration dependent correlation functions see C. L. Brooks III and S. A. Adelman, J. Chem. Phys. 77, 484 (1982)., J. Chem. Phys.
14.A descrition of the MTGLE approach to problems in condensed phase chemical reaction dynamics in simple physical terms is given in S. A. Adelman and C. L. Brooks III, J. Phys. Chem. 86, 1511 (1982).
15.A recent review of the MTGLE theory and how it is used to study chemical reaction dynamics in liquid solution is given in S. A. Adelman, Adv. Chem. Phys. 53, 61 (1983).
16.For example, see the following classic works on stochastic dynamics: (a) S. Chandrasekhar, Rev. Mod. Phys. 15, 1 (1943);
16.(b) M. Wang and G. Uhlenbeck, Rev. Mod. Phys. 17, 323 (1945)., Rev. Mod. Phys.
17.The excitation wavelength determines the initial excited electronic states, assuming Frank—Condon transitions with energies in near resonance with that of the exciting laser pulse. See Refs. 6, 8, and 24.
18.The cavity potential describes the average I‐solvent interaction for relative I‐I separation R. in the absence of the direct interaction between the two iodine atoms. In general, one would also expect to depend upon the iodine electronic state. However, since this latter dependence is not known, we have used the same (calculated for X state iodine) for all three electronic states.
19.Linear response theory is developed in general quantum mechanical form by R. Kubo, J. Phys. Soc. Jpn. 12, 570 (1957).
20.See, for example, R. F. Grote and J. T. Hynes, J. Chem. Phys. 73, 2715 (1980)
21.D. W. Oxtoby, Adv. Chem. Phys. 47, Part 2, 487 (1981).
22.D. W. Oxtoby, Adv. Chem. Phys. 40, 1 (1979).
23.This is because the MTGLE parameters are essentially constant when both iodine atoms are inside a common cage. There is a solvent‐dependent minimum value of the I—I relative separation, below which the parameters ( etc.) cease to change with decreasing R. In the case of as the solvent, Thus, the MTGLE parameters have their 3 Å values for For ethane as the solvent, Therefore, if there would exist nonlinear effects on the subsequent dynamics due to choice of cage lag model, the best chance to observe them would be with as the solvent. A comparison of the profiles obtained with several different cage lag models and with as the solvent revealed no essential difference in the dynamics subsequent to the initial photolysis step.
24.J. Tellinghuisen, J. Chem. Phys. 58, 282 (1973).
25.W. H. Miller, J. Chem. Phys. 48, 464 (1968).
26.B. Martire and R. G. Gilbert, Chem. Phys. 56, 241 (1981).
27.A. J. Stace and J. N. Murrell, Mol. Phys. 33, 1 (1977).
28.G. Herzberg, Spectra of Diatomic Molecules, 2nd ed. (Van Nostrand, New York, 1950), Table 39, p. 541, footnote a for
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