Abstract

The melting of monolayers of isotopically labeled n-alkanes on Pt(111) surfaces has been followed by reflection−absorption infrared (RAIR) spectroscopy, and the results are compared with those of an earlier study of the unlabeled molecules (J. Phys. Chem. 1995, 99, 15629−15278). Temperature-dependent studies show that monolayers of the n-octane isotopolog, CD3(CH2)6CD3, melt on Pt(111) from a two-dimensionally ordered phase to one having one-dimensional order (“hexatic”) near 220 K, a temperature essentially identical to that seen for unlabeled n-octane. The RAIR spectra of the labeled molecules generally confirm (but in one case clarify an overly simplistic interpretation of) the assignments of the bands made in the earlier study. Specifically, the assignment of a low-frequency “softened” mode near 2760 cm-1 to a νCH stretch for proximal (i.e., surface-contacting) methylene C−H bonds has been verified. A feature near 2900 cm-1 had previously been assigned to a distal methylene C−H stretch, and the line w...

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