Abstract
Vibrational sum-frequency spectroscopy and surface tensiometry have been used to study the adsorption of m- and p-cyanophenol at the air-water interface. Spectra of the cyano (CN) group under different polarization schemes are utilized to determine its hydrogen bonding environment and orientation. For both isomers, it is found that the cyano group is hydrogen bonded at the interface but that the CN orientation is independent of surface density. The average CN tilt angle (theta(0)), however, is found to differ between the isomers, such that the CN group points down toward the aqueous phase for m-cyanophenol (theta(0) = 96-106 degrees ) but points up toward the vapor phase for the p-cyanophenol (theta(0) = 65-80 degrees ). In addition, this average tilt angle is distributed over a narrow range, sigma(0) < 10 degrees for the meta isomer and sigma(0) < 16 degrees for the para isomer.
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