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Geometric factor corrections (tooling factors) for the placement of the QCM crystal relative to the sample and absolute fluxes were calibrated using AFM-measured film thicknesses at the sample and QCM crystal locations.
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-1 for M-OH stretches. For example, see: Infrared and Raman Characteristic Group Frequencies, 3rd ed.; Socrates, G., Ed.; John Wiley and Sons: New York, 2001. In our experiments at grazing incidence on Au metal surfaces, we observe LO modes. Since the frequencies of LO modes under these conditions are shifted toward the high end of the overall absorption envelope, our spectral peaks will be shifted to higher frequencies than for the TO modes.
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The IR electric field screening calculations used model structures based on uniform, parallel, noninteracting isotropic layers of [Au substrate]/ [organic film of ∼2 nm thickness (the model IR active oscillator represents the C-H stretching mode region of the SAM film)]/[metal overlayer of variable thickness]. The numerical calculations were based on previously developed algorithms. See: Parikh, A. N.; Allara, D. L. J. Chem. Phys. 1992, 96, 927-945. The n and k values of the complex refractive indices of the metals were taken from several sources:
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(b) Handbook of Optical Constants; Palik, E. D., Ed.; Academic Press: San Diego, 1998. Since no optical constant data were available for Ca, the values for Mg were used on the basis that they are adjacent in group II and so will have similar optical properties.
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Palik, E.D.1
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2 (in our case), and alkyl chains with increasing conformational disorder. Although it is not possible to assign the relative contributions from the spectra, this observation suggests that Ca may react with the more disordered SAM chains. This may occur if there was a preference for the Ca atoms to react with the chains in SAM defect regions, leaving some fraction of the more ordered chains relatively intact.
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Attempts were not made to fit the attenuation of the Au 4f peak areas as a function of metal coverage by an overlayer growth morphology model (e.g., layer by layer vs islanding) because the chemical composition and topography (i.e., clusters vs uniform conformal deposition) of the overlayers are not known, and there is a lack of quantitative information about the mean free paths of the photoelectrons in the various possible product phases (e.g., carbides, oxides, and hydrides).
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Initial deposition of Ti causes a small shift to a slightly higher binding energy with a gradual return shift as coverage continues to increase. This behavior is consistent with previous reports about metal depositions on SAMs (see refs 3, 5, 7, and 42).
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Baer, D. R.; Marmorstein, A. M.; Williford, R. E.; Blanchard, D. L. Surf. Sci. Spec. 1992, 1, 80-86.
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2 is extremely hydroscopic and reaction with atmospheric water and oxygen could not be avoided before acquiring a TOF SIMS spectrum.
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