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12944336331
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note
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0 + δ(x) + κΓ(x), where δ(x) represents a position-dependent stochastic fluctuation in the local resistivty, Γ(x) is the surface number density, and κ is a constant that depends on the chemical identity of the adsorbate. However, the stochastic and adsorption terms comprise typically an effect ≤ 5%, so they are neglected in this treatment.
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12944320092
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note
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In these experiments, 3 mm × 75 mm Au films were deposited onto glass microscope slides and configured with four contacts sealed under epoxy to facilitate immersion of the narrow Au WE's.
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32
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12944320093
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note
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The spread of the surface energy gradient over nearly 400 mV in in-plane potential is most likely due to surface roughness of the Au films on glass, as anticipated by Porter and co-workers in ref 41.
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33
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12944299047
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note
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The small volume of the SPR flow-cell required the use of a Ag/ AgCl quasi-reference electrode prepared by contacting the working solution to a 0.5 M KOH/MeOH solution containing the Ag/AgCl electrode reference with a Au wire.
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34
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12944319597
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note
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+-pumped Ti-Sapphire laser. Imaging was performed with a 512 512 pixel CCD camera.
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37
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0027262068
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39
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12944325567
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note
-
The series of images in Figure 2 are numerically subtracted from an original exposure of the biased Au film to cancel a small (relative to the SAM) electroreflectance contribution. The reflection angle was set such that dark regions correspond to OT-covered Au and light regions to bare Au.
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40
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12944280011
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note
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The difference in half-widths of the desorption waves in Figures 1 and 2 can be attributed to differences in surface preparation. Figure 2 data were obtained on a carefully annealed evaporated Au film, producing Nernstian width waves with minimal separation. Figure 1 data were acquired on unannealed Au, because the magnitude of the gradient, i.e., Δ cos θ, is larger on unannealed Au than on annealed Au.
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41
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0000696823
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Weisshaar, D. E.; Lamp, B. D.; Porter, M. D. J. Am. Chem. Soc. 1992, 114, 5860-5862.
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42
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12944313803
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note
-
-1. An in-plane potential gradient of this magnitude would necessitate an electrode length of the order of 10's of μm to avoid difficulties with solvent electrolysis and gas evolution.
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