Affiliation: | Department of Chemistry, Faculty of Science, Kobe University, Nada-ku, Kobe 657 Japan Departamento de Estructura Atómico-Molecular y Espectroscopía, Facultad de Ciencias Químicas, Universidad Complutense, 28040 Madrid Spain |
Abstract: | The IR and Raman spectra of ethyl trichloroacetate (E-TCA) and its deuterate (E-TCA-d5) have been measured in the liquid, glassy and crystalline states. Vibrational assignment was made by referring to isotopic wavenumber-shift, characteristic group frequencies of related esters and with the aid of a normal coordinate calculation on E-TCA and E-TCA-d5. It is suggested that in the liquid and glassy states there exist two molecular forms (trans—trans—trans and trans—trans—gauche) with regard to the internal rotations about the ClC---C---O---CH2CH3 axis, and that the former persists in the crystalline state. The band pairs of E-TCA and the other ethyl esters are discussed in relation to the nature and number of rotational axes, effect of the heavy trichloromethyl group, and enhancement of band intensity by vibrational coupling. |