Abstract
Polarization modulation Fourier transform infrared reflection absorption spectroscopy (PM-FTIRRAS) has been applied to study the structure of gold surfaces modified with organic monolayers by spontaneous adsorption. It is found that the infrared spectrum of a hydrophobic octadecanethiol monolayer changes little from the ex situ spectrum when placed in the presence of deuterium oxide solution. The changes that are observed in the infrared spectrum are characteristic of rotations about the terminal methyl group, consistent with organic monolayers in contact with aqueous solutions. In the presence of acetonitrile solutions, the in situ spectrum contains few changes beyond those observed in the aqueous solutions, but nothing that indicates a dramatic alteration of the monolayer structure. A slight peak shift to higher wavenumber and additional peak asymmetry for the asymmetric methylene stretch in the presence of acetonitrile may indicate some amount of hydration of the outer portions of the monolayer not observed in the aqueous solutions. This infrared data is consistent with previous spectroscopic observations but deviates from electrochemical measurements made with these monolayer surfaces.
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