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Volumn 36, Issue 17, 1997, Pages 3689-3701

Analysis of Exchange Interaction and Electron Delocalization as Intramolecular Determinants of Intermolecular Electron-Transfer Kinetics

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EID: 0001281577     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic961298q     Document Type: Article
Times cited : (59)

References (104)
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    • note
    • This expression is based on a description of nuclear motion in semiclassical approximation and is valid for kT > hv. A full quantum-mechanical treatment is more laborious but may reveal some new pecularities of the electron-transfer characteristics of the systems that we intend to study. However, we believe that the main qualitative conclusions of our study remain valid.
  • 36
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    • Cammack, R., Ed.; Academic Press: San Diego. CA
    • Holm, R. H. In Iron-Sulfur Proteins: Cammack, R., Ed.; Academic Press: San Diego. CA, 1992; Vol. 38, pp 1-71.
    • (1992) Iron-Sulfur Proteins , vol.38 , pp. 1-71
    • Holm, R.H.1
  • 49
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    • This condition does not imply that the trapping forces are weak, since the resonance energies may be big
    • This condition does not imply that the trapping forces are weak, since the resonance energies may be big.
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    • Williams, R. J. P. Chapter l in Electron Transfer in Biology and the Solid State; Johnson, M. K. King, R. B., Kurtz, D. M., Kutal, C., Norton, M. L., Scott, R. A., Eds.; American Chemical Society: Washington, DC, 1990; Vol. 226.
    • (1990) Electron Transfer in Biology and the Solid State , vol.226
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    • note
    • eff may alter the electronic wave function. Therefore, these vibrations can change the electronic state energies and become active in the electron transfer. For the sake of clarity, we have chosen the present treatment. An analysis based on anharmonic potentials is in progress.
  • 75
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    • note
    • 34 However, in the context of Anderson's theory for antiferromagnetic exchange, the levels described by eqs 18 and 26 represent the lower half of a more extended space of interacting states which includes the metalmetal charge-transfer configurations. The barycenter of the energies is conserved only when the full space is considered. Therefore, the barycenters of the energies given in eqs 18 and 26 are a function of J and J′ , respectively.
  • 77
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    • note
    • deloc, provided that the constant energy shift, δ , defined in eq 24. has the same value in the two reactions. In addition, the net value of -ΔG ° is lowered by resonance interaction (B ≠ 0). Delocalization effects on rate constant can be favorably studied in se If-exchange reactions since contributions to ΔG*from resonance stabilization in donor and acceptor cancel.
  • 79
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    • This assumption is arbitrary but has little impact on the general trend in the results. When the transfer from the second site is set equal to that from the first site, the value for the rate constant is doubled
    • This assumption is arbitrary but has little impact on the general trend in the results. When the transfer from the second site is set equal to that from the first site, the value for the rate constant is doubled.
  • 80
    • 0642316382 scopus 로고    scopus 로고
    • Under the assumption of strong double exchange, the upper state of any pair of delocalized states with equal spin is high in energy therefore, its contribution to the electron-transfer process can be ignored
    • Under the assumption of strong double exchange, the upper state of any pair of delocalized states with equal spin is high in energy therefore, its contribution to the electron-transfer process can be ignored.
  • 81
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    • note
    • s,s-1/2 for J′ = 0, while the two barriers differ for J′≠ 0. Since the spin-dependent factors given in eq 30 have larger values for the + sign than for the - sign, only the barriers obtained for the + sign are presented.
  • 82
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    • note
    • red.
  • 83
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    • note
    • loc given in eqs 33 and 34a differ even for J = J′ = 0 due to the different character (viz. localized and delocalized, respectively) of the corresponding S = 9/A ground states.
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    • Figure 2, ref 53
    • Figure 2, ref 53.
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    • note
    • The preexponential factor reflects also the electrostatic repulsion between the 3+ charged hole donor and the 2+ charged acceptor. This interaction is affected by electron delocalization in the mixedvalence panner of the reaction. The large size of the molecules containing the cluster mitigates this effect of delocalization by a mechanism analogous to that described for the solvation energy in the Introduction. This supports the assumption that the preexponetial factor is constant.


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