A SUBPICOSECOND, SUBNANOSECOND AND STEADY-STATE STUDY OF DIFFUSION-INFLUENCED FLUORESCENCE QUENCHING

被引:112
作者
EADS, DD
DISMER, BG
FLEMING, GR
机构
[1] UNIV CHICAGO,DEPT CHEM,CHICAGO,IL 60637
[2] UNIV CHICAGO,JAMES FRANCK INST,CHICAGO,IL 60637
关键词
D O I
10.1063/1.459177
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
Subpicosecond and subnanosecond time resolved experiments are combined with steady-state fluorescence measurements to examine the diffusion influenced fluorescence quenching reaction of rhodamine B and ferrocyanide. The classic models of Smoluchowski, and Collins and Kimball are unable to consistently explain both the rapid initial decay and the slower decay seen at long times (> 1 ns) in the experimental data. Neither the short nor the long time data can be reconciled with the steady-state data using these models. Better agreement is found between the data and a simple model incorporating a position dependent intrinsic reaction rate [A. Szabo, J. Chem. Phys. 93, 6929 (1989)] in addition to a diffusional rate. This model suggests a rate of electron transfer for the rhodamine B-ferrocyanide system of (27.5 ± 4 ps)-1. Use of a bare Coulomb potential between reactants is found to be inappropriate in all of the models investigated. © 1990 American Institute of Physics.
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页码:1136 / 1148
页数:13
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