The Infra-Red Absorption Spectra of CH3OD and CH2DOD

The infra-red absorption spectra of CH3OD and CH2DOD between 2.5μ and 24μ have been examined with a KBr prism spectrometer, and with appropriate gratings. The observed bands represent all of the fundamental vibrations except the one of lowest frequency which is associated with torsional vibrations about the C–O bond. Since these molecules depart only slightly from axial symmetry, the bands, with the exception of three due to the hydroxyl radical, correspond in position and appearance to those of the methyl halides. The rotational structure for the 10μ band (v5) of CH3OD has been resolved, and partial resolution is obtained in some other bands. The band v5 in CH2DOD has two components arising probably from two forms of the molecule in which the hydroxyl D atom occupies different valleys of the threefold potential. The deformation vibration (v7) is single for CH3OD but has four components in CH2DOD, indicating a separation of levels which for the former molecule are degenerate. A comparison of the frequencies obtained with gaseous and liquid samples indicates large displacements of the bands arising from the hydroxyl valence and deformation vibrations, the former toward greater wave-lengths in the liquid, and the latter toward smaller wave-lengths.