Abstract
From solution of the time-dependent wave equation by specifying the ψ(t) function in the form of a linear combination ai(t)ψi+ad(t)ψd+aj(t)ψj (ψi, ψd, ψj are the wave functions corresponding to localization of the electron on the donor, the intermediate link, and the acceptor), we obtain an expression for the electron transfer probability in a system consisting of six components: one direct transfer and five interference components. We have studied the effect of electronic structure and vibrational motion of the components of the system on the probability components. This has allowed us to find the dependence of the electron transfer probability on the ionization potential or the electron affinity of the intermediate link, playing the role of a catalyst or inhibitor of the process.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Literature cited
H. Taube and H. Myers, “Evidence for bridged activated complex for electron transfer reaction,” J. Am. Chem. Soc.,76, no. 8, 2103–2111 (1954).
J. Halpern and L. Orgell, “Oxidation-reduction reactions in ionizing solvents,” Disc. Farad. Soc.,29, No. 1, 32–45 (1960).
Yu. I. Kharkats, A. K. Madumarov, and M. A. Vorotyntsev, “Application of the density matrix method in the quantum mechanical calculation of the bridge-assisted electron transfer probability in polar media,” J. Chem. Soc. Faraday Trans. II,70, No. 9, 1578–1590 (1974).
V. A. Zasukha and S. V. Volkov, “Theory of electron transfer in systems with an intermediate link,” Teor. Éksp. Khim.,21, No. 3, 288–293 (1985).
V. A. Zasukha and S. V. Volkov, “Theory of electron transfer in donor-acceptor pairs,” Int. J. Quantum Chem.,16, No. 4, 761–767 (1979).
V. A. Zasukha and S. V. Volkov, “Theory and mechanism of electron transfer in a condensed medium at high temperatures with allowances for change in vibrational frequencies,” Int. J. Quantum Chem.,28, No. 1, 17–26 (1985).
V. A. Zasukha and S. V. Volkov, “Theory and mechanism of electron transfer at low temperatures,” Int. J. Quantum Chem.,29, No. 3, 1815–1824 (1986).
V. A. Zasukha and S. V. Volkov, “Selection rules for electron transfer between impurities in crystals,” Phys. Status Solidi b,130, No. 6, 65–68 (1985).
V. A. Zasukha, “Selection rules for electron transfer between impurities in crystals and the method of fractional parentage coefficients,” J. Phys. C.,20, No. 13, 1925–1933 (1987).
V. A. Zasukha, “Selection rules for electron phototransfer between impurities in crystals,” Chem. Phys.,125, No. 1, 1–8 (1989).
V. A. Zasukha, “Theory of bridge-assisted electron transfer in systems with an intermediate link,” Teor. Éksp. Khim.,22, No. 5, 524–530 (1986).
P. A. M. Dirac, The Principles of Quantum Mechanics [Russian translation], Fizmatgiz, Moscow (1960).
S. V. Volkov and V. A. Zasukha, Quantum Chemistry of Coordination Condensed Systems [in Russian], Nauk. Dumka, Kiev (1985).
A. F. Lubchenko, Quantum Transitions in Impurity Centers of Solids [in Russian], Nauk. Dumka, Kiev (1978).
F. Basolo and R. G. Pearson, Mechanisms of Inorganic Reactions [Russian translation], Mir, Moscow (1971).
V. A. Zasukha, “Direct and indirect two-electron transfer in condensed media,” Chem. Phys. Lett.,144, No. 4, 382–386 (1988).
V. A. Zasukha, “Theory of electron phototransfer in a condensed medium,” Opt. Spektrosk.,61, No. 1, 68–74 (1986).
Author information
Authors and Affiliations
Additional information
Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 134–142, March–April, 1989.
Rights and permissions
About this article
Cite this article
Zasukha, V.A. Theory of bridge-assisted electron transfer in systems with an intermediate link at high temperatures. Theor Exp Chem 25, 119–127 (1989). https://doi.org/10.1007/BF01134999
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF01134999