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Influence Of Solvent On The Interfacial Structure Of Self-Assembled Alkanethiol Monolayers, Mark Anderson, Mark Evaniak, Minhui Zhang

Mark R. Anderson

Polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) is used to study the structure of octadecanethiol, tetradecanethiol, and decanethiol monolayers in the presence of air, deuterium oxide, and acetonitrile-d3. It is found that the structure of the monolayer is dependent on both the adjacent environment and the initial structural order of the monolayer. In the D2O solutions, spectral changes are similar for the three monolayers and are characteristic of interaction predominantly between the solvent and the terminal portion of the monolayers. This correlates with electrochemical capacitance measurements that indicate little permeation of the aqueous electrolyte in the monolayer, even with the …