COMPARISON OF EXPERIMENTAL AND THEORETICAL ELECTRONIC MATRIX-ELEMENTS FOR LONG-RANGE ELECTRON-TRANSFER

被引:112
作者
SIDDARTH, P [1 ]
MARCUS, RA [1 ]
机构
[1] CALTECH, NOYES LAB CHEM PHYS, PASADENA, CA 91125 USA
关键词
D O I
10.1021/j100370a046
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The dependence of electron-transfer rates on the number of intervening groups is treated by using a single calculational method for four separate series of compounds: a biphenylyl donor and a 2-naphthyl acceptor, separated by various rigid saturated hydrocarbon bridges, a dimethoxynaphthyl donor and a dicyanovinyl acceptor, separated by norbornyl groups, a Ru(NH3)5II donor and a Ru(NH3)5III acceptor, separated by different numbers of dithiaspiro rings, and an Os(NH3)5II donor and an Ru(NH3)5III acceptor separated by an isonicotinyl plus a variable number of proline groups, which again provide a rigid spacer. The results for the electron-transfer matrix element obtained both with direct diagonalization and with the partitioning method are compared with each other, with the experimental results and, where available, with previously calculated results. © 1990 American Chemical Society.
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页码:2985 / 2989
页数:5
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