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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

Title	Determination of Reorganization Energy from the Temperature Dependence of Electron Transfer Rate Constant for Hydroquinone-tethered Self-assembled Monolayers (SAMs)
Author	Wonchoul Park, Hun-Gi Hong*
Keywords	Hydroquinone-tethered SAM, Reorganization energy, Temperature dependence, Rate constant, Heterogeneous electron transfer
Abstract	The temperature dependence on the electron transfer rate constant (k_app) 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 [k_app/T^1/2] 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 k_app 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.
Page	381 - 385
Full Text	PDF

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