The Case for Methyl Group Precession Accompanying Torsional Motion

Abstract

For molecules containing a methyl group, high precision fits of rotational line data (microwave spectra) that encompass several torsional states require considerably more constants than are required in comparable rigid molecules. Many of these additional terms are ‘torsion-rotation interaction’ terms, but their precise physical meaning is unclear. In this paper, we explore the physical origins of many of these additional terms in the case where the methyl group is attached to a planar frame. We show that torsion-vibration coupling, which has been observed in toluene and several substituted toluenes, provides the dominant contribution to a number of the torsion-rotation constants in toluene. It is further demonstrated that this coupling is intimately related to precession of the methyl group. A number of the constants required in the high resolution fits of rotational line data are shown to arise as a natural consequence of methyl precession. By considering several molecules whose rotational line spectra have been fit to high precision, we demonstrate that the experimental evidence is consistent with the occurrence of methyl group precession. Quantum chemistry calculations of the optimised molecular structures at key torsional angles provide further evidence that methyl precession occurs. There is both a torsional angle dependent tilt of the Cmethyl-frame bond and of the methyl group principal rotation axis relative to the Cmethyl-frame bond.