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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 27, Number 3
BKCSDE 27(3)
March 20, 2006 

Determination of Reorganization Energy from the Temperature Dependence of Electron Transfer Rate Constant for Hydroquinone-tethered Self-assembled Monolayers (SAMs)
Wonchoul Park, Hun-Gi Hong*
Hydroquinone-tethered SAM, Reorganization energy, Temperature dependence, Rate constant, Heterogeneous electron transfer
The temperature dependence on the electron transfer rate constant (kapp) for hydroquinone redox center in H2Q(CH2)nSH-SAMs (n = 1, 4, 6, 8, 10, and 12) on gold electrode was investigated to obtain reorganization energy (λ) using Laviron’s formalism and Arrhenius plot of ln [kapp/T1/2] vs. T-1 based on the Marcus densityof-states model. All the symmetry factors measured for the SAMs were relatively close to unity and rarely varied to temperature change as expected. The electron tunneling constant (β) determined from the dependence of the kapp on the distance between the redox center and the electrode surface gives almost the same β values which are quite insensitive to temperature change. Good linear relationship of Arrhenius plot for all H2Q(CH2)nSH-SAMs on gold electrode was obtained in the temperature range from 273 to 328 K. The slopes in Arrhenius plot deduced that λ of hydroquinone moiety is ca. 1.3-1.4 eV irrespectively of alkyl chain length of the electroactive SAM.
381 - 385
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