MARCUS INVERTED REGION - NATURE OF DONOR-ACCEPTOR PAIRS AND FREE-ION YIELDS

被引：44

作者：

BURGET, D

JACQUES, P

VAUTHEY, E

SUPPAN, P

HASELBACH, E

机构：

[1] ENSCMU,PHOTOCHIM GEN LAB,CNRS,URA 431,3 RUE A WERNER,F-68093 MULHOUSE,FRANCE

[2] UNIV FRIBOURG,INST PHYS CHEM,CH-1700 FRIBOURG,SWITZERLAND

来源：

JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS | 1994年 / 90卷 / 17期

关键词：

D O I：

10.1039/ft9949002481

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 free ion yield (PHI(R)) resulting from the fluorescence quenching of 9,10-dicyanoanthracene (DCA) by various electron donors in acetonitrile has been studied using ns laser photoconductivity. The influence of the chemical nature of the doors is established in a general manner. For a given oxidation potential E(ox)(D/D+), the rate constant of geminate ion recombination, k(bac), decreases significantly as the electronic delocalization of the donor increases. As a consequence multiple Marcus plots are observed in the inverted region. These plots show decreasing curvature when going from stilbenes to amines as donors. This 'fan effect' is tentatively explained by considering the detailed roles of the parameters V, lambda and hnu in the Marcus model.

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页码：2481 / 2487

页数：7

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