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 language | English |
|---|---|
| Pages (from-to) | 5712-5715 |
| Number of pages | 4 |
| Journal | Journal of Physical Chemistry |
| Volume | 95 |
| Issue number | 15 |
| Publication status | Published - 1991 |
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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 journal › Article
}
TY - JOUR
T1 - Ultrafast measurements on direct photoinduced electron transfer in a mixed-valence complex
AU - Walker, Gilbert C.
AU - Barbara, Paul F.
AU - Doorn, Stephen K.
AU - Dong, Yuhua
AU - Hupp, Joseph T
PY - 1991
Y1 - 1991
N2 - 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.
AB - 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.
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M3 - Article
VL - 95
SP - 5712
EP - 5715
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 15
ER -