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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electron transfer
Metals
valence
Kinetics
Electrons
kinetics
Absorption spectroscopy
metals
Raman spectroscopy
Charge transfer
vibration mode
Rate constants
absorption spectroscopy
charge transfer
vibration
shift
coefficients
predictions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Ultrafast measurements on direct photoinduced electron transfer in a mixed-valence complex. / Walker, Gilbert C.; Barbara, Paul F.; Doorn, Stephen K.; Dong, Yuhua; Hupp, Joseph T.

In: Journal of Physical Chemistry, Vol. 95, No. 15, 1991, p. 5712-5715.

Research output: Contribution to journalArticle

Walker, GC, Barbara, PF, Doorn, SK, Dong, Y & Hupp, JT 1991, 'Ultrafast measurements on direct photoinduced electron transfer in a mixed-valence complex', Journal of Physical Chemistry, vol. 95, no. 15, pp. 5712-5715.
Walker, Gilbert C. ; Barbara, Paul F. ; Doorn, Stephen K. ; Dong, Yuhua ; Hupp, Joseph T. / Ultrafast measurements on direct photoinduced electron transfer in a mixed-valence complex. In: Journal of Physical Chemistry. 1991 ; Vol. 95, No. 15. pp. 5712-5715.
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