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Charge Transfer Reactions and Solvation Dynamics

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Ultrafast Dynamics of Chemical Systems

Part of the book series: Understanding Chemical Reactivity ((UCRE,volume 7))

Abstract

In this article, we offer a perspective on solvation dynamics from the point of view of chemical reactions, and in particular from an initial viewpoint of heavy particle charge transfer reactions. These reactions include SN2 nucleophilic displacements — X - + RY → XR + Y - SN1 unimolecular ionizations —RX →, R + + dipolar isomerizations, and (with a certain elasticity of definition) ion pair interconversion. Here the solvation dynamics act to influence the motion of the reacting solute nuclear coordinate(s), and thus to influence the reaction rate. The primary reactive coordinate is a nuclear coordinate of the solute.

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References

  1. Hynes, J. T., in The Theory of Chemical Reaction Dynamics,Vol. IV, M. Bear, e.d (CRC Press, Boca Raton, FL, 1985), p. 171.

    Google Scholar 

  2. For some general reviews, see Ref. 1 and Truhlar, D. G., Hase, W. L., and Hynes, J. T., J. Phys. Chem. 87, 2664 (1983); Hynes, J. T., Anna. Rev. Phys. Chem. 36, 573 (1985); Berne, J. B., Borkovec, M., and Sträub, J. E., J. Phys. Chem. 92, 3711 (1988); Hänngi, P., Talkner, P., and Borkovec, M., Rev. Mod. Phys. 62, 251 (1990). In addition, the special issue Chem. Phys. 152,nos. 1 and 2 (1991) is devoted to friction in liquid state reactions.

    Article  CAS  Google Scholar 

  3. Whitnell, R. M. and Wilson, K. R., Adv. Comp. Chem. 4, 67 (1993).

    CAS  Google Scholar 

  4. For reviews, see, e.g., Simon, J. D., Acc. Chem. Res. 21,128 (1988); Kosower, E. M. and Huppert, D., Annu. Rev. Phys. Chem. 37, 127 (1986); Barbara, P. F. and Jarzeba, W., Adv. Photochem. 15,(1990); Marconcelli, M., MacInnis, J., and Fleming, G. R., Science,243,1674 (1989); Bagchi, B., Annu. Rev. Phys. Chem. 37, 127 (1986); Maroncelli, M., J. Molec. Liq.,in press. Some representative experimental studies include Su, S.-G. and Simon, J. D., J. Phys. Chem.91,2693 (1987); Chem. Phys. Lett. 158,423 (1989); Kahlow, M. A., Kang, T. J., and Barbara, P. F., J. Chem. Phys. 86, 3183 (1987); Kahlow, M. A., Jarzeba, W., Kang, T. J., and Barbara, P. F., ibid. 90, 151 (1988); Marconcelli, M. and Fleming, G. R., ibid. 86, 6221 (1987); Castner Jr., E. W., Marconcelli, M., and Fleming, G. R., ibid. 86, 1090 (1987); Simon, J. D. and Su, S.-G., Chem. Phys. 152, 143 (1991).

    Article  CAS  Google Scholar 

  5. Grote, R. F. and Hynes, J. T., J. Chem. Phys. 76, 2715 (1980). (For some recent discussions of the GH rate equation and especially the associated GLE from a theoretical point of view, see Tarjus, G. and Kivelson, D., Chem. Phys. 152, 153 (1991) and Ref. 7c below.)

    Article  Google Scholar 

  6. Bergsma, J. P., Reimers, J. R., Wilson, K. R., and Hynes, J. T., J. Chem. Phys. 85, 5625 (1986).

    Article  CAS  Google Scholar 

  7. Bergsma, J.R, Gertner, B. J., Wilson, K. R., and Hynes, J. T., J. Chem. Phys. 86 1356 (1987); (b) Gertner, B. J., Bergsma, J. P., Wilson, K. R., Lee, S., and Hynes, J. T., ibid. 86, 1377 (1987); (c) Gertner, B. J., Wilson, K. R., and Hynes, J. T., ibid. 90, 3537 (1989); (d) Gertner, B. J., Whitnell, R. M., Wilson, K. R., and Hynes, J. T., J. Amer. Chem. Soc. 113,74(1991).

    Article  CAS  Google Scholar 

  8. Ciccotti, G., Ferrano, ML, Hynes, J. T., and Kapral, R., J. Chem. Phys. 93, 7137 (1990); (b) Rey, R. and Guardia, E., J. Phys. Chem. 96, 4712 (1992).

    Article  CAS  Google Scholar 

  9. Keirstead, W. P., Wilson, K. R., and Hynes, J. T., J. Chem. Phys. 95, 5256 (1991).

    Article  CAS  Google Scholar 

  10. Zichi, D. A., Ciccotti, G., Hynes, J. T., and Ferrano, M., J. Phys. Chem. 93, 2184 (1989).

    Article  Google Scholar 

  11. Zhu, S. B., Lee, J., and Robinson, G. W, J. Phys. Chem. 92, 2401 (1988); (b) Berne, B. J., Borkovec, M., and Sträub, J. E., ibid. 92, 3711 (1988); (c) Roux, B. and Karplus, M. ibid. 95, 4845 (1991).

    Article  CAS  Google Scholar 

  12. Tucker, S. and Truhlar, D., J. Amer. Chem. Soc. 112,3347 (1990).

    Article  CAS  Google Scholar 

  13. Bagchi, B. and Oxtoby, D. W, J. Chem. Phys. 78, 2735 (1983).

    Article  CAS  Google Scholar 

  14. Ashcroft, J., Besnard, M., Aquada, V., and Jonas, J., Chem. Phys. Lett. 110, 430 (1984).

    Article  Google Scholar 

  15. Zeglinski, D. M. and Waldeck, D. H., J. Phys. Chem. 923, 692 (1988); Sivakumar, N., Hoburg, E. A., and Waldeck, D. H., ibid. 90, 2305 (1989); Park, N. S. and Waldeck, D. H., ibid

    Article  Google Scholar 

  16. McManis, G. E. and Weaver, M. J., J. Chem. Phys. 90, 1720 (1989).

    Article  CAS  Google Scholar 

  17. Zwan, G. van der and Hynes, J. T., J. Chem. Phys. 76, 2993 (1982).

    Article  Google Scholar 

  18. Zwan, G. van der and Hynes, J. T., J. Chem. Phys. 76, 4174 (1983); Chem. Phys. 90, 21, (1984).

    Article  Google Scholar 

  19. Kramers, H. A., Physica 7, 284 (1940).

    Article  CAS  Google Scholar 

  20. See, e.g., Newton, M. D. and Sutin, N., Annu. Rev. Phys. Chem. 35, 437 (1984).

    Article  CAS  Google Scholar 

  21. For recent deveopments, one may consult: Dynamics and Mechanics of Photoinduced Electron Transfer and Related Phenomena, Mataga, N., Okada, T., and Masuhara, H., eds., (Elsevier, Amsterdam, 1992).

    Google Scholar 

  22. For an early example of the use of AEcoordinates, see Warshel, A., J. Phys. Chem. 86, 2218 (1982).

    Article  CAS  Google Scholar 

  23. Hynes, J. T., J. Phys. Chem. 90, 370 (1986).

    Google Scholar 

  24. Marcus, R. A., J. Chem. Phys. 24, 966 979 (1956).

    Article  CAS  Google Scholar 

  25. Zusman, L. D., Chem. Phys. 49, 295 (1980).

    Article  CAS  Google Scholar 

  26. Zichi, D. A., Kim, H. J., Carter, E. A., and Hynes, J. T., unpublished.

    Google Scholar 

  27. See, e.g., Hynes, J. T. and Deutch, J. M., in Physical Chemistry, an Advanced Treatise, Vol. IIB, eds. H. Eyring, W. Jost, and D. Henderson (Academic, New York, 1985), p. 153.

    Google Scholar 

  28. Zwan, G. van der and Hynes, J. T., J. Phys. Chem. 89, 4181 (1985).

    Article  Google Scholar 

  29. Rips, I. and Jortner, J., J. Chem. Phys. 87, 2090 (1987).

    Article  CAS  Google Scholar 

  30. Maroncelli, M., Caster Jr., E. W, Bagchi, B., and Fleming, G. R., Faraday Disc. Chem. Soc. 85, 199 (1988).

    Article  CAS  Google Scholar 

  31. Fonseca, T., J. Chem. Phys. 91, 2869 (1989); Chem. Phys. Lett. 162, 491 (1989).

    Article  CAS  Google Scholar 

  32. Carter, E. A. and Hynes, J. T., J. Chem. Phys. 94, 5961 (1991); see also, Hynes, J. T., Carter, E. A., Ciccotti, G., Kim, H. J., Zichi, D. A., Ferrario, M., and Kapral, R., in Perspectives in Photosynthesis,Jortner, J. and Pullman, B., eds. (Kluwer, Dordrecht, 1990), p. 133.

    Article  CAS  Google Scholar 

  33. Marconcelli, M. and Fleming, G. R., J. Chem. Phys. 86, 6221 (1987); 89, 5044 (1987).

    Article  Google Scholar 

  34. Fonseca, T. and Landanyi, B. M., J. Phys. Chem. 95, 2116 (1991).

    Article  CAS  Google Scholar 

  35. Lee, S. and Hynes, J. T., J. Chem. Phys. 88, 6853, 6863 (1988); Zichi, D. A. and Hynes, J. T., ibid. 88, 2513 (1988); Kim, H. J. and Hynes, J. T., J. Am. Chem. Soc. 114, 10508, 10528 (1992).

    Article  CAS  Google Scholar 

  36. Grote, R. R., Zwan, G. van der, and Hynes, J. T., J. Phys. Chem. 88, 4676 (184).

    Google Scholar 

  37. Houston, S. E., ’Rossky, P. J., and Zichi, D., J. Am. Chem. Soc. 111,5680 (1989).

    Article  Google Scholar 

  38. Hwang, J.-K., King, G., Creighton, S., and Warshel, A., J. Am. Chem. Soc. 110, 5297 (1988).

    Article  CAS  Google Scholar 

  39. Bader, J. S. and Chandler, D., Chem. Phys. Lett. 157,501 (1989).

    Article  CAS  Google Scholar 

  40. Levy, R. M., Kitchen, D. B., Blair, J. T., and Krogh-Jespersen, K., J. Phys. Chem. 94,4470 (1990), Blair, J. T, Krogh-Jespersen, K., and Levy, R. M., ibid. 111, 6948 (1989); (b) Benjamin, I. and Wilson, K. R., ibid. 95, 3514 (1991).

    Article  CAS  Google Scholar 

  41. Maroncelli, M., J. Chem. Phys. 94, 2084 (1991).

    Article  CAS  Google Scholar 

  42. Bruehl, M. and Hynes, J. T., J. Phys. Chem. 96, 4068 (1992).

    Article  CAS  Google Scholar 

  43. Carter, E. A. and Hynes, J. T., J. Phys. Chem. 93, 2184 (1989); (b) Fonseca, T., Ladanyi, B. M., and Hynes, J. T., ibid. 96,4085 (1992); (c) Fonseca, T. and Ladanyi, B., J. Mol. Liq.,in press; (d) King, G. and Warshel, A., J. Chem. Phys. 93, 8682 (1990).

    Article  CAS  Google Scholar 

  44. Rosenthal, S. J., Xie, X., Du, M., and Fleming, G. R., J. Chem. Phys. 95,4715 (1991).

    Article  CAS  Google Scholar 

  45. Smith, B. B., Kim, H. J., Borgis, D., and Hynes, J. T., in Dynamics and Mechanisms of Photoinduced Electron Transfer and Related Phenomena, N. Mataga, T. Okada, and H. Masuhara, eds., (Elsevier, Amsterdam, 1992). p. 39; (b) Smith, B. B., Staib, A., and Hynes, J. T., Chem. Phys. 176, 521 (1993).

    Google Scholar 

  46. Alexandrov, I. V. and Gabrielyan, R. G., Mol. Phys. 37, 1963 (1979); Friedman, H. L. and Newton, M. D., Faraday Discuss. Chem. Soc. 74, 73 (1982); Calef, D. F. and Wolynes, P. G., J. Phys. Chem. 87, 3387 (1983); Sumi, H. and Marcus, R. A., J. Chem. Phys. 84, 4272 (1986); Sparpaglioni, M. and Mukamel, S., J. Chem. Phys. 88, 3263 (1988); (b) Rips, I. and Jortner, J., ibid. 87, 2090 (1987); (c) Dakhnovskii, Yu. I. and Ovchinikov, A. A., Mol. Phys. 58, 237 (1986); Zusman, L. D., Chem. Phys. 51, 119 (1988); Murillo, M. and Cukier, R. I., J. Chem. Phys. 89, 6736 (1988); Fonseca, T., ibid. 91, 2869 (1989); Zhou, Y., Friedman, H. L., and Stell, G., Chem. Phys. 152, 185 (1991); McManis, G. E., Gochev, A., and Weaver, M. J., ibid. 152, 107 (1991).

    Article  Google Scholar 

  47. Borgis, D., Lee, S., and Hynes, J. T., Chem. Phys. Lett. 162, 19 (1989); Borgis, D. and Hynes, J. T., J. Chem. Phys. 94, 3619 (1991); Chem. Phys. 170, 315 (1993).

    Article  CAS  Google Scholar 

  48. There are other simulations of aspects of electron transfer reactions, but they do not address the issues considered here. See, e.g., (a) Warshel, A., J. Chem. Phys. 86, 2218 (1982); Hwang, J. and Warshel, A., J. Am. Chem. Soc. 109,715 (1987); (b) Halley, J. W. and Hautmann, J., Phys. Rev. B38,11704 (1988); (c) Kuharski, R. A., Bader, J. S., Chandler, D., Sprik, M., Klein, M. L., and Impey, R. W., J. Chem. Phys. 89, 3248 (1988); (d) Gonzalez-Lafont, A., Lluch, J. M., Oliva, A., and Bertran, J., in Chemical Reactivity in Liquids,M. Moreau and P. Turq, eds. (Plenum, New York, 1988), p. 197; (e) Hwang, J. K., Creighton, S., King, G., Whitney, D., and Warshel, A., J. Chem. Phys. 89, 859 (1988).

    Article  CAS  Google Scholar 

  49. Fonseca, T. and Ladanyi, B. M., to be submitted. The low barrier ET reaction case is generally, though not always, a more faithful adherent to the full spectrum of solvation dynamics: see also Tominaga, K., Walker, G. C, Kang, T. J., Barbara, P. R., and Fonseca, T., J. Phys. Chem. 95, 10485 (1991); Kang, T. J., Jarzeba, W, Barbara, P. R, and Fonseca, T, Chem. Phys.149, 81 (1990), in Perspectives in Photosynthesis,J. Jortner and B. Pullman, eds. (Kluwer, Dordrecht, 1990).

    Google Scholar 

  50. Whitnell, R. M., Wilson, K. R., and Hynes, J. T, J. Phys. Chem. 94, 8625 (1990); J. Chem. Phys. 96,5354 (1992).

    Article  CAS  Google Scholar 

  51. Johnson, A. E., Levinger, N. E., and Barbara, P. B., 96,7841 (1992); Whitnell, R. M. and Benjamin, I., Chem. Phys. Lett. 204,45 (1993); Owrutsky, J. C, Kim, Y. R., Li, M., Sarisky, M. J., and Hochstrasser, R. M., ibid. 184,368 (1991).

    Google Scholar 

  52. Bruehl, M. and Hynes, J. T, Chem. Phys. 175, 205 (1993).

    Article  CAS  Google Scholar 

  53. Gertner, B. J., Ando, K., Bianco, R., and Hynes, J. T, Chem. Phys., in press.

    Google Scholar 

  54. Hynes, J. T, unpublished.

    Google Scholar 

  55. See, e.g., Fonseca, T, Gomes, J. A. N. F., Grigolini, P., and Marchesoni, F, Adv. Chem. Phys. 62, 389 (1985).

    Article  CAS  Google Scholar 

  56. Nee, T. and Zwanzig, R., J. Chem. Phys. 52,6353 (1970); Hubbard, J. B. and Wolynes, P. G., ibid.69, 998 (1978); Wolynes, P. G., Ann. Rev. Phys. Chem. 31,345 (1980); Madden, P. A. and Kivelson, D., Adv. Chem. Phys. 56, 479 (1984).

    Article  CAS  Google Scholar 

  57. Simon, J. D. and Thompson, P. A., J. Chem. Phys. 92, 2891 (1990); Alavi, D. S., Hartman, R. S., and Waldeck, D. H., ibid. 94, 4509 (1991).

    Article  CAS  Google Scholar 

  58. However, the situation improves for the continuum description when finite size effects are accounted for: Alavi, D. S. and Waldeck, D. H., J. Chem. Phys. 94, 6196 (1991); Hartman, R. S., Alavi, D. S., and Waldeck, D. H., J. Phys. Chem. 95,7872 (1991).

    Article  CAS  Google Scholar 

  59. Zwan, G. van der and Hynes, J. T., Chem. Phys. 152,169 (1991); Chapman, C. F. and Maroncelli, M., J. Phys. Chem. 95,9095 (1991); Ittah, V. and Huppert, D., Chem. Phys. Lett. 173,496 (1990); Huppert, D., Itah, V., and Kosower, E. ML, ibid. 159, 267 (1989).

    Article  Google Scholar 

  60. Sebastian, K., J. Chem. Phys. 90, 5056 (1989); Smith, B. B. and Hynes, J. T., ibid.in press; Schmickler, W, J. Electroanal Chem. 230,43 (1987); Morgan, J. D. and Wolynes, P. G., J. Phys. Chem. 91,874 (1981).

    Article  CAS  Google Scholar 

  61. Benjamin, I., J. Chem. Phys. 95,3698 (1991).

    Article  CAS  Google Scholar 

  62. Jarzeba, W, Walker, G. C, Johnson, A. E., and Barbara, P. F., Chem. Phys. 152,57 (1991).

    Article  CAS  Google Scholar 

  63. Scherer, N. F., Zeigler, L., and Fleming, G. R., J. Chem. Phys. 96, 5544 (1992); Nelson, K. A. and Williams, L. R., Phys. Rev. Lett. 58, 745 (1987).

    Article  CAS  Google Scholar 

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  1. Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, 80309-0215, USA

    James T. Hynes

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  1. Department of Chemistry, University of California, San Diego, La Jolla, California, USA

    John D. Simon

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Hynes, J.T. (1994). Charge Transfer Reactions and Solvation Dynamics. In: Simon, J.D. (eds) Ultrafast Dynamics of Chemical Systems. Understanding Chemical Reactivity, vol 7. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-0916-1_13

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  • DOI: https://doi.org/10.1007/978-94-011-0916-1_13

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