FREE-ENERGY DEPENDENCE OF THE INTRINSIC RATE OF ELECTRON-TRANSFER IN DIFFUSIONAL QUENCHING OF TRANS-STILBENE-S1 BY ELECTRON-DEFICIENT OLEFINS

被引:32
作者
ANGEL, SA [1 ]
PETERS, KS [1 ]
机构
[1] UNIV COLORADO,DEPT CHEM & BIOCHEM,BOULDER,CO 80309
关键词
D O I
10.1021/j100162a033
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 quenching of the first excited singlet states of trans-stilbene and 4,4'-dimethyl-trans-stilbene by acrylonitrile, fumaronitrile, and tetracyanoethylene has been examined by picosecond laser spectroscopy. The intrinsic rate constant of electron transfer is separated from the diffusion rate constant by applying the Collins and Kimball formalism for time-dependent rate constants. The intrinsic rates of electron transfer are correlated with the free energy changes for electron transfer, and it is found that the correlation does not follow the predictions of Marcus' adiabatic electron-transfer theory.
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页码:3606 / 3612
页数:7
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