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

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

Northwestern University

Research output: Contribution to journal › Article › peer-review

118 Citations (Scopus)

Abstract

A direct measurement of the kinetics of intramolecular photoinduced metal-metal charge transfer has been made, i.e. (NH₃)₅Ru^IIINCFe^II(CN) ₅^- ⇄_kET^hv (NH₃)₅Ru^IINCFe^III(CN) ₅^- 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 → ∞, equal to (8 ± 3) × 10¹¹ s^-1. This is close to the theoretical predictions from the model of Sumi and Marcus (classical vibrational modes), k_ET,SM = 10¹³ and 5 × 10¹² s^-1, and from the model of Jortner and Bixon (quantum mechanical vibrations), k_ET,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

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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@article{ce58c160ba8845569c4175d19e8f56ab,

title = "Ultrafast measurements on direct photoinduced electron transfer in a mixed-valence complex",

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.",

author = "Walker, {Gilbert C.} and Barbara, {Paul F.} and Doorn, {Stephen K.} and Yuhua Dong and Hupp, {Joseph T}",

year = "1991",

language = "English",

volume = "95",

pages = "5712--5715",

journal = "Journal of Physical Chemistry",

issn = "0022-3654",

publisher = "American Chemical Society",

number = "15",

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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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