ULTRAFAST MEASUREMENTS ON DIRECT PHOTOINDUCED ELECTRON-TRANSFER IN A MIXED-VALENCE COMPLEX

被引:134
作者
WALKER, GC
BARBARA, PF
DOORN, SK
DONG, YH
HUPP, JT
机构
[1] UNIV MINNESOTA,DEPT CHEM,MINNEAPOLIS,MN 55455
[2] NORTHWESTERN UNIV,DEPT CHEM,EVANSTON,IL 60208
关键词
D O I
10.1021/j100168a002
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
A direct measurement of the kinetics of intramolecular photoinduced metal-metal charge transfer has been made, i.e. [GRAPHICS] where the solvent is H2O or D2O and k(ET) signifies the reverse-electron-transfer (ET) rate coefficient. The apparent reverse-electron-transfer kinetics are nonexponential with a limiting rate constant, k(lim) = k(t) where t --> infinity, equal to (8 +/- 3) x 10(11) s-1. This is close to the theoretical predictions from the model of Sumi and Marcus (classical vibrational modes), k(ET,SM) = 10(13) and 5 x 10(12) s-1, and from the model of Jortner and Bixon (quantum mechanical vibrations), k(ET,JB) = 1.2 x 10(12) s-1. The parameters required for these theories were estimated by resonance Raman spectroscopy, static absorption spectroscopy, and recently published transient Stokes shift measurements.
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页码:5712 / 5715
页数:4
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