Cluster Models for Condensed-Phase Electron Transfer Processes

  • M. D. Newton
Part of the NATO ASI Series book series (NSSB, volume 283)


Electron transfer (ET) processes pose intriguing challenges to electronic structure theories for donor/acceptor (D/A) interactions [1]. Recent theoretical advances are providing a unified understanding of D/A coupling in a number of closely related processes of the 1-electron (e.g., photoelectron and electron transmission spectroscopy, and charge transfer spectroscopy, as well as thermal and photoinitiated ET) and 2-electron (e.g., magnetic exchange and triplet energy transfer) type [1]. In the modelling of such processes in condensed phases, discrete molecular clusters containing local D and A sites as well as any intervening material have played a crucial role. In the case of intermolecular ET, the cluster is a super-molecule complex corresponding to the transition state for the process [2–4]. In the present paper we focus on recent progress in the mechanistic analysis of ET reactions based on discrete cluster models and illustrate the approach with the results of several computational studies.


Electron Transfer Process Redox Pair Redox Partner Transition State Theory Encounter Complex 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Newton, M. D., Chem. Revs. (in press).Google Scholar
  2. 2.
    (a) Logan, J.; Newton, M. D. J. Chem. Phys. 78, 4086 (1983);CrossRefGoogle Scholar
  3. 2a.
    (b) Newton, M. D. J. Phys. Chem. 90, 3734 (1986);CrossRefGoogle Scholar
  4. 2b.
    (c) Newton, M. D. J. Phys. Chem. 92, 3049 (1988);CrossRefGoogle Scholar
  5. 2c.
    (d) Newton, M. D. in Perspectives in Photosynthesis, J. Jortner, B. Pullman, Eds., Kluwer Academic Publishers, 1990, p. 157;CrossRefGoogle Scholar
  6. 2d.
    (e) Newton, M. D.; Ohta, K; Zhong, E. J. Phys. Chem, 95, 2317 (1991).CrossRefGoogle Scholar
  7. 3.
    Larsson, S. J. Phys. Chem. 88, 1321 (1984).CrossRefGoogle Scholar
  8. 4.
    Ohta, K.; Morokuma, K. J. Phys. Chem. 91, 401, (1987).CrossRefGoogle Scholar
  9. 5a.
    (a) Marcus, R. A. J. Chem. Phys. 24, 966 (1956);CrossRefGoogle Scholar
  10. 5b.
    (b) Marcus, R. A. J. Chem. Phys. 24, 979 (1956).CrossRefGoogle Scholar
  11. 6a.
    (a) Newton, M. D.; Sutin, N. Ann. Rev. Phys. Chem. 35, 437–480 (1984);CrossRefGoogle Scholar
  12. 6b.
    (b) Sutin, N. Prog. Inorg. Chem. 30, 441 (1983).CrossRefGoogle Scholar
  13. 7.
    Calef, D. F.; Wolynes, P. G. J. Phys. Chem. 87, 3387–3400 (1983).CrossRefGoogle Scholar
  14. 8.
    Hynes, J. T. J. Phys. Chem. 86, 3701–3706 (1986).CrossRefGoogle Scholar
  15. 9.
    Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 811, 265–322 (1985).Google Scholar
  16. 10.
    (a) Larsson, S. J. Am. Chem. Soc. 103, 4034 (1981);CrossRefGoogle Scholar
  17. 10.
    (b) Larsson, S. J. Chem. Soc., Faraday Trans. 279, 1375–1388 (1983);Google Scholar
  18. 10.
    (c) Larsson, S. Chemica Scripta 28A, 15–20(1988).Google Scholar
  19. 11.
    (a) Ohta, K.; Closs, G. L.; Morokuma, K.; Green, N. J. J. Am. Chem. Soc. 108, 1319–1320 (1986);CrossRefGoogle Scholar
  20. (b).
    Farazdel, A.; Dupuis, M.; Clementi, E.; Aviram, A. J. Am. Chem. Soc. 112, 4206 (1990).CrossRefGoogle Scholar
  21. 12.
    (a) Beratan, D. N.; Onuchic, J. N.; Hopfield, J. J. J. Chem. Phys. 86, 4488 (1987);CrossRefGoogle Scholar
  22. (b).
    Kuki, A.; Wolynes, P. Science 236, 1647 (1987).CrossRefGoogle Scholar
  23. 13.
    McConnell, H. M. J. Chem. Phys. 35, 508 (1961).CrossRefGoogle Scholar
  24. 14.
    Kuznetsov, A. M.; Ulstrup, J. J. Chem. Phys. 75, 2047 (1981).CrossRefGoogle Scholar
  25. 15.
    Goodenough, J. B. Magnetism in the Chemical Bond, John Wiley & Sons, New York, 1963.Google Scholar
  26. 16.
    Buhks, E.; Bixon, M.; Jortner, J.; Navon, G. Inorg. Chem. 18, 2014 (1979).CrossRefGoogle Scholar
  27. 17.
    (a) Newton, M. D. ACS Symp. Ser. D. R. Salahub, M. C. Zerner, Eds., 394, 3783 (1989);Google Scholar
  28. 17a .
    (b) Newton, M. D. J. Phys. Chem. 95, 30 (1991).CrossRefGoogle Scholar
  29. 18.
    Plato, M.; Möbius, K.; Michel-Beyerle, M. E.; Bixon, M.; Jortner, J. J. Am. Chem. Soc. 110, 7279–7285 (1988).CrossRefGoogle Scholar
  30. 19.
    Scherer, P. O. J.; Fischer, S. F. J. Phys. Chem. 93, 1633–1637 (1989).CrossRefGoogle Scholar
  31. 20.
    Mikkelsen, K. V.; Dalgaard, E.; Swanstom, P. J. Phys. Chem. 91, 3081–3092 (1987).CrossRefGoogle Scholar
  32. 21.
    Landau, L. Phys. Z. Sowjet 2, 46 (1932);Google Scholar
  33. 21a.
    Zerner, C. Proc. Roy. Soc. London Ser. A, 696 (1932).Google Scholar
  34. 22.
    (a) Zerner, M. C.; Loew, G. H.; Kirchner, R. F.; Mueller-Westerhoff, U. T. J. Am. Chem. Soc. 102, 589 (1980);CrossRefGoogle Scholar
  35. 22a.
    (b) Anderson, W. P.; Edwards, W. D.; Zerner, M. C. Inorg. Chem. 25, 2728–2732 (1986).CrossRefGoogle Scholar
  36. 23.
    (a) King, H. F.; Stanton, R. E.; Kim, H.; Wyatt, R. E.; Parr, R. G. J. Chem. Phys. 47, 1936 (1967);CrossRefGoogle Scholar
  37. 23a.
    (b) Amos, A. T.; Hall. C. G. Proc. Roy. Soc. London, Ser. A, A263, 483 (1961).Google Scholar
  38. 24.
    Krishnan, R.; Frisch, M. J.; Pople, J. A. J. Chem. Phys. 72, 4244 (1980).CrossRefGoogle Scholar
  39. 25.
    Larsson, S.; Stahl, K.; Zerner, M. C. Inorg. Chem. 25, 3033–3037 (1986).CrossRefGoogle Scholar
  40. 26.
    (a) Tembe, B. L.; Friedman, H. L.; Newton, M. D. J. Chem. Phys. 76, 1490 (1982);CrossRefGoogle Scholar
  41. 26a.
    (b) Friedman, H. L.; Newton, M. D. Faraday Discuss. Chem. Soc. 74, 73–81 (1982).CrossRefGoogle Scholar
  42. 27.
    Kuharski, R. A.; Bader, J. S.; Chandler, D.; Sprik, M.; Klein, M. L. J. Chem. Phys. 89, 3248–3257 (1988).CrossRefGoogle Scholar
  43. 28.
    McManis, G. E.; Nielson, R. M.; Gochev, A.; Weaver, M. J. J. Am. Chem. Soc. 111, 5533 (1989).CrossRefGoogle Scholar
  44. 29.
    McManis, G. E.; Nielson, R. M.; Weaver, M. J. Inorg. Chem. 27, 1827–1829 (1988).CrossRefGoogle Scholar
  45. 30.
    Hammershoi, A.; Geselowitz, D.; Taube, H. Inorg. Chem. 23, 979 (1984).CrossRefGoogle Scholar
  46. 31.
    Wilson, R. B.; Solomon, E. I. J. Am. Chem. Soc. 102, 4085 (1980).CrossRefGoogle Scholar
  47. 32.
    (a) Anderson, P. W. Phys. Rev. 79, 350 (1950);CrossRefGoogle Scholar
  48. 32a.
    (b) Anderson, P. W. J. Chem. Phys. 115, 2, (1959).Google Scholar
  49. 33.
    Wang, Y. J.; Newton, M. D.; Davenport, J. W.; to be published.Google Scholar

Copyright information

© Plenum Press, New York 1992

Authors and Affiliations

  • M. D. Newton
    • 1
  1. 1.Department of ChemistryBrookhaven National LaboratoryUptonUSA

Personalised recommendations