The Raman and infrared spectra for the C4, C8, C12, and C16 carboxylic acid series were obtained at liquid nitrogen temperatures, in the 2900 cm−1 spectral region and were compared to spectra for selected branched and straight chain alkane systems. For hexadecanoic acid-d3 the Fermi resonance interaction between the CD3 symmetric stretching mode and the overtone level of the CD3 asymmetric deformation vibration was examined as a function of physical state. In this example of a negative Fermi resonance perturbation, in which the lower frequency overtone component is more intense than the higher frequency fundamental, the coupling increases as the system passes from either the matrix isolated species or solution phase to the polycrystalline state. The spectra of the carboxylic acid series, as well as the spectra of 2,2,4-trimethyl pentane and n-octane, suggest that in the 2900 cm−1 region an analogous Fermi resonance coupling exists between the CH3 symmetric stretching vibration at ∼2938 cm−1 and the 2871 cm−1 overtone transition of the CH3 asymmetric deformation. Unfortunately, the 2930–2940 cm−1 region for the solid systems is further complicated by transitions attributed to crystal interactions. Although the Fermi interaction for the methyl group has been recognized in the simpler halomethane system, for example, it has not been previously discussed in the more general context of significantly larger branched and straight chain molecules. Comparisons of the carboxylic acid spectra in the 2900 cm−1 region have also led to assignments for the α-CH2 (adjacent to the carbonyl group) and the ω-CH2 (adjacent to the methyl group) C–H stretching modes.
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