An Origin of Complicated Infrared Spectra of Perfluoroalkyl Compounds Involving a Normal Alkyl Group

Abstract

Perfluoroalkyl (Rf) compounds containing a normal alkyl group often yield highly complicated infrared (IR) spectra especially in the C–F stretching vibration (νC–F) region. To reveal the reason behind this, the IR p-polarized multiple-angle incidence resolution spectrometry (pMAIRS) is employed to measure a monolayer of CF3(CF2)9(CH2)3COOH deposited on a silicon substrate. The compound is known to spontaneously aggregate to form a molecular assembly with the closest packing, in which the molecules are oriented perpendicular to the substrate. The IR pMAIRS spectra apparently prove that the complexity of the νC–F region is due to the normal alkyl part directly connected to the Rf group because the carbons in the Rf group are vibrated as a coupled oscillator, and the oscillation of the alkyl part propagates to the Rf part along the molecular axis.