The effects of torsion–vibration coupling on rotational spectra: Toluene reinterpreted and refitted

Jason Gascooke, Warren Lawrance

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    14 Citations (Scopus)

    Abstract

    A re-examination of rotational line positions for toluene is reported, motivated by the recent observation that the methyl internal rotor states are perturbed by torsion-vibration coupling to vibrational mode M20 (Gascooke et al., 2015). We demonstrate that the data can be fit equally well including or excluding torsion-vibration coupling. The torsion-vibration model required to account for the torsional band positions is thus shown to be consistent with the rotational line positions reported. It is found that including torsion-vibration coupling leads to changes in the values of the rotational and torsional constants, most significantly for AF, AF′, F and V6, as well as the higher order constants, with those involving powers of m, K and their cross-terms most affected. Expressions for these effects are provided based on a perturbation expansion, which shows the links between the two models. A primary indicator for the presence of torsion-vibration coupling is AF′ being significantly different to the rotational constant for the frame, AF, and changing with m. Examination of published AF′/AF ratios for several substituted toluenes suggests that torsion-vibration coupling is widespread in such molecules. Torsion-vibration coupling has been directly observed through local perturbations to torsional levels in substituted toluenes with both 3- and 6-fold torsion potentials, indicating that it will also affect rotational and torsional constants in molecules with a 3-fold barrier. This indicates that the assumption that the small amplitude vibrations can be ignored when considering the large amplitude methyl rotation requires reassessment.

    Original languageEnglish
    Pages (from-to)53-63
    Number of pages11
    JournalJOURNAL OF MOLECULAR SPECTROSCOPY
    Volume318
    DOIs
    Publication statusPublished - 1 Dec 2015

    Keywords

    • Internal rotation
    • Large amplitude motion
    • Methyl rotation
    • Microwave spectroscopy

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