Torsion-vibration interactions determined from (far) infrared spectra.

Abstract

Observations of the torsional and low-lying vibrational-torsional states of toluene, p-fluorotoluene, and m-fluorotoluene using the technique of two dimensional laser induced fluorescence (2D-LIF) have revealed interactions between the methyl torsion and low frequency out-of-plane methyl wagging vibration. These interactions can change the values of constants extracted from the analysis of rotational spectra, which usually assume that the large amplitude torsional motion can be treated independent of the small amplitude vibrations. Since out-of-plane methyl wagging modes will be present whenever a methyl group is attached to a planar frame, this type of torsion-vibration interaction is potentially widespread; it is thus important to establish the extent and strength of this type of interaction. 2D-LIF is limited to molecules that fluoresce from excited electronic states, and to explore interactions between torsion and methyl wagging vibrations in a wide range of molecules necessitates developing alternative experimental approaches. Infrared absorption spectroscopy is one such approach. It is shown that for the low torsional barrier case, the torsional sequence bands accompanying the out-of-plane methyl wagging transition provide a sensitive probe of the interaction. As an illustration, the far infrared absorption spectrum of toluene in the region of the M20 band (∼205cm-1) is presented and analyzed. The torsional sequence structure provides insight into the higher torsional states (up to m = 7) in the ground vibrational state and M20. An analysis of these bands enables the torsion-vibration coupling and torsional constants to be extracted. A general method to analyze such spectra is presented.