Abstract
Intramolecular electron transfer rates for ion formation and recombination in bridged donor/acceptor systems have been determined using fluorescence lifetime and transient absorption measurements. The data show a weak dependence of the rate on the donor/acceptor distance as well as a dependence on the electronic structure of the spacer. These findings are interpreted as evidence for an electronic coupling between donor and acceptor through the bridge. The magnitude of the electronic coupling is estimated on the basis of Extended-Hückel molecular orbital calculations for model structures simulating the electronic interaction in the donor/acceptor systems. The calculations can semiquantitatively explain ratios of rates for different spacers between donor and acceptor. Intramolecular and solvent reorganization energies are derived from the temperature dependence of the ion formation and the ratio of the rates for ion formation and recombination.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
J. Deisenhofer, O. Epp, K. Miki, R. Huber, and H. Michel, J. Mol. Biol. 180, 385 (1984).
J. Breton, J.L. Martin, A. Migus, A. Antonetti, and A. Olscag, Proc. Nat. Acad. Sci. (1986), in press.
J. Halpern and L.E. Orgel, Discuss. Faraday Soc. 29, 32 (1960).
H.M. McConnell, J. Chem. Phys. 35, 508 (1961).
S. Larsson, J. Am. Chem. Soc. 103, 4034 (1981).
J. Jortner and M. Bixon, Proceedings of the Conference on Structure and Functions of Proteins, Philadelphia, March 1985, in press.
H. Michel, O. Epp, and J. Deisenhofer (1986), in preparation.
H. Heitele, M.E. Michel-Beyerle, and G. Wegner, to be published.
V.G. Levich, Adv. Electrochem. Electrochem. Eng. 4, 249 (1966).
N.R. Kestner, J. Logan, and J. Jortner, J. Chem. Phys. 78, 2148 (1974).
R.P. Van Duyne and S.F. Fischer, Chem. Phys. 5, 183 (1974).
J.Ulstrup, “Charge Transfer Processes in Condensed Media”, Springer Verlag Berlin, 1979.
H. Heitele and M.E. Michel-Beyerle, J. Am. Chem. Soc. 107, 8286 (1985).
N. Remy-Richter, M. Volk, A. Ogrodnik, H. Heitele, and M.E. Michel-Beyerle, in preparation.
J.R. Miller, J.V. Beitz, and R.K. Huddleston, J. Am. Chem. Soc. 106, 5057 (1984).
N. Sutin, Prog. Inorg. Chan. 30, 441 (1983)
M.D. Newton and N. Sutin, Ann. Rev. Phys. Chem. 35, 437 (1984); and references therein
H. Heitele and M.E. Michel-Beyerle in: “Antennas and Reaction Centers of Photosynthetic Bacteria”, ed. M.E. Michel-Beyerle, Springer Series in Chemical Physics 42, p. 250, Springer Verlag, Berlin 1985.
A.D. Joran, B.A. Leland, G.G. Geller, J.J. Hopfield, and P.B. Dervan, J. Am. Chem. Soc. 106, 6090 (1984).
B.A. Leland, A.D. Joran, P.M. Felker, J.J. Hopfield, A.H. Zewail, and P.B. Dervan, J. Phys. Chem. 89, 5571 (1985).
J.M. Warman, M.P. de Haas, M.N. Paddon-Row, E. Cotsaris, N.S. Hush, H. Oevering, and J.W. Verhoeven, Nature 320, 615 (1986).
S. Larsson, J. Chem. Soc., Faraday Trans. 2, 79, 1375 (1983).
D.N. Beratan and J.J. Hopfield, J. Am. Chem. Soc. 106, 1584 (1984).
R.A. Marcus, J. Chem. Phys. 24, 966 (1956)
R.A. Marcus, J. Chem. Phys. 43, 679 (1965).
R.A. Marcus and N. Sutin, Biochim. Biophys. Acta 811, 265 (1985).
J. Jortner, J. Chem. Phys. 64, 4860 (1976).
B.S. Brunschwig, J. Logan, M.D. Newton, and N. Sutin, J. Am. Chem. Soc. 102, 5798 (1980); and references therein.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1986 D. Reidel Publishing Company
About this paper
Cite this paper
Heitele, H., Michel-Beyerle, M.E., Finckh, P., Rettig, W. (1986). Role of Intramolecular Bridges on Electron Transfer in Donor/Acceptor Systems. In: Jortner, J., Pullman, B. (eds) Tunneling. The Jerusalem Symposia on Quantum Chemistry and Biochemistry, vol 19. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4752-8_27
Download citation
DOI: https://doi.org/10.1007/978-94-009-4752-8_27
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-010-8611-0
Online ISBN: 978-94-009-4752-8
eBook Packages: Springer Book Archive