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M = ±0.02. The SAM-functionalized QCM crystal and Au reference crystals were placed side by side, the same distance from the deposition source and the sample QCM holder temperature controlled at ∼25°C (the approximate SAM sample temperatures in the actual analysis experiments) by use of circulated water. The SAM QCM crystals (Cold Springs R&D, Syracuse, NY) were highly polished on one side to an rms roughness (tapping mode AFM) of 0.1-0.2 nm, which resulted in the QCM SAM surfaces having near identical rms roughnesses to those of the SAMs prepared on silicon substrates. Both QCMs had movable shutters to independently control access of the metal flux to the surfaces. Just prior to a set of measurements, the sample was blocked while the reference shutter was opened to allow the Ti flux to strike the reference QCM surface and condense many layers of Ti to provide a fresh Ti surface with unit efficiency in condensing Ti atoms. Subsequently both shutters were opened to make continuous measurements of the total flux delivered (reference QCM) and the amount condensed on the SAM.
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In general, because of the heterogeneous nature of the deposited Ti (e.g., see AFM data), quantitative analysis of the various core level peaks in the XPS spectra was not performed.
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It is interesting to note that if there were a kinetic isotope effect for Ti reaction with a C-H(D) bond, one would expect that the C-D bonds would be attacked more slowly (by factors reaching as high as nearly half an order of magnitude), all other factors being equal. For such an isotope effect, one would expect in the case of a fully protiated molecule that the top part of the SAM would react even more rapidly (selectively) compared to the bottom part than indicated in Figure 3 for the molecule with the deuterated top.
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