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要旨:
Sum-frequency vibrational spectroscopy has been used to determine the structure of monolayers of the cationic surfactant, hexadecyltrimethylammonium p-tosylate (C16TA+Ts-), at the surface of water. Selective deuteration of the cation or the anion allowed the separate detection of sum-frequency spectra of the surfactant and of counterions that are bound to the monolayer. The p-tosylate ions are oriented with their methyl groups pointing away from the aqueous subphase and with the C2 axis tilted, on average, by 30−40° from the surface normal. The vibrational spectra of C16TA+ indicate that the number of gauche defects in the monolayer does not change dramatically when bromide counterions are replaced by p-tosylate. The ends of the hydrocarbon chains of C16TA+ are, however, tilted much further from the surface normal in the presence of p-tosylate than in the presence of bromide. A quantitative analysis of the sum-frequency spectra requires a knowledge of the molecular hyperpolarizability tensor: the role of ab initio calculations and Raman spectroscopy in determining the components of this tensor is discussed.
