Torsional splitting in the ν5 fundamental infrared band of CH3CD3 and 13CH3CD3

The nu (5) fundamental (C-C stretching) of CH3CD3 shows a resolved torsional structure, caused by perturbations due mainly to the linear dependence of the torsional potential barrier on the normal coordinate Q(5). We were able to analyze this structure and to assign vibration-rotation transition wavenumbers for all five torsional components, classified according to the symmetry species of the G(18)((3)) extended molecular group. The torsional splitting pattern is qualitatively similar to that of a nondegenerate vibrational state with an even number of excited torsional quanta nu (6). Explorative calculations show that the main perturber system should consist of the torsional components of the vibrational ground state correlating with nu (6) = 3 in the high barrier limit. The strength of the perturbation on the E-r0 torsional components of nu (5) increases rapidly with r, the E-40 component being the most affected. The observed transition wavenumbers can be reasonably fitted by a simplified model containing independent effective vibration-rotation parameters for the five different torsional components of nu (5), for both CH3CD3 and (CH3CD3)-C-13.The trend of the determined values of the effective vibrational wavenumbers and rotational parameters over the torsional components supports the proposed vibration-torsion interaction mechanism, responsible for the observed torsional splittings. A strong anomaly observed in the rotational intensity distribution of nu (5) is discussed. (C) 2001 Academic Press.