Ultrafast measurements on direct photoinduced electron transfer in a mixed-valence complex

Gilbert C. Walker, Paul F. Barbara, Stephen K. Doorn, Yuhua Dong, Joseph T Hupp

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Abstract

A direct measurement of the kinetics of intramolecular photoinduced metal-metal charge transfer has been made, i.e. (NH3)5RuIIINCFeII(CN) 5-kEThv (NH3)5RuIINCFeIII(CN) 5- where the solvent is H2O or D2O and kET signifies the reverse-electron-transfer (ET) rate coefficient. The apparent reverse-electron-transfer kinetics are nonexponential with a limiting rate constant, klim = k(t) where t → ∞, equal to (8 ± 3) × 1011 s-1. This is close to the theoretical predictions from the model of Sumi and Marcus (classical vibrational modes), kET,SM = 1013 and 5 × 1012 s-1, and from the model of Jortner and Bixon (quantum mechanical vibrations), kET,JB = 1-2 × 1012 s-1, The parameters required for these theories were estimated by resonance Raman spectroscopy, static absorption spectroscopy, and recently published transient Stokes shift measurements.

Original languageEnglish
Pages (from-to)5712-5715
Number of pages4
JournalJournal of Physical Chemistry
Volume95
Issue number15
Publication statusPublished - 1991

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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