Analysis of Kinetic Models for the Tunnel Electron Transfer Reactions. Reaction Kinetics for Various Radial and Angular Dependences of the Tunneling Probability Full article
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Chemical Physics
ISSN: 0301-0104 |
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Output data | Year: 1981, Volume: 61, Number: 3, Pages: 351-364 Pages count : 14 DOI: 10.1016/0301-0104(81)85154-3 | ||||||
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Abstract:
A new version of the “stepwise” approximation used in kinetic models for the long range electron transfer reactions is suggested. Using this approach the effects on the kinetics of these reactions of such factors are examined as a more complicated dependence (compared to the commonly used exponential one) of the tunneling probability, w, on the distance between the reagents as well as the angular dependence of w. For many practically important situations taking account of the above factors is shown to have no significant effect on the form of the reaction kinetics for both the pairwise and random spatial distributions of the reagents. However, the relations between the parameters aef and νcf in the expression for the tunneling distance R* = 1/2aef In νcft, which can be determined from the experimental kinetics, and similar theoretical parameters νo and a that are involved in the expressions for w are found to be different for various types of the radial and the angular dependences of w. It is shown that when the orbitals between which the electron transfer takes place are located at sites removed from the geometric centers of the reactants the values of νef can exceed by many orders of magnitude the characteristic frequency of the electron movement in molecules νe ≈ 1013 s−1.
Cite:
Doktorov A.B.
, Khairutdinov R.F.
, Zamaraev K.I.
Analysis of Kinetic Models for the Tunnel Electron Transfer Reactions. Reaction Kinetics for Various Radial and Angular Dependences of the Tunneling Probability
Chemical Physics. 1981. V.61. N3. P.351-364. DOI: 10.1016/0301-0104(81)85154-3 WOS Scopus РИНЦ
Analysis of Kinetic Models for the Tunnel Electron Transfer Reactions. Reaction Kinetics for Various Radial and Angular Dependences of the Tunneling Probability
Chemical Physics. 1981. V.61. N3. P.351-364. DOI: 10.1016/0301-0104(81)85154-3 WOS Scopus РИНЦ
Dates:
Submitted: | Aug 18, 1980 |
Accepted: | May 20, 1981 |
Published print: | Oct 15, 1981 |
Published online: | Nov 15, 2001 |
Identifiers:
Web of science | WOS:A1981MQ47300010 |
Scopus | 2-s2.0-0000551132 |
Elibrary | 30811939 |
Chemical Abstracts | 1981:625969 |
Chemical Abstracts (print) | 95:225969 |
OpenAlex | W1997234862 |