Approaching the free rotor limit: extremely low methyl torsional barrier observed in the microwave spectrum of 2,4-dimethylfluorobenzene

• Published in: Physical chemistry chemical physics : PCCP 2023-12, Vol.26 (1), p.42-411
• Main Authors: Khemissi, Safa, Schwell, Martin, Kleiner, Isabelle, Nguyen, Ha Vinh Lam
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Fluorine; Fourier transforms; Frequency ranges; Microwave spectrometers; or physical chemistry; Physics; Quantum chemistry; Rotation; Rotors; Theoretical and; Toluene; Torsion
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d3cp04748b

The microwave spectrum of 2,4-dimethylfluorobenzene was recorded using a molecular jet Fourier transform microwave spectrometer in the frequency range from 2.0 to 26.5 GHz. The spectral assignment and modeling were challenging due to the large tunnelling splittings resulting from the very low barrier to internal rotation of the p -methyl group that approaches the free rotor limit. Internal rotation splittings arising from two inequivalent o - and p -methyl groups were observed, analysed and modelled using the modified version of the XIAM code and the BELGI-C s -2Tops code, giving a root-mean-square deviation of 549.1 kHz and 4.5 kHz, respectively, for a data set of 885 rotational lines. The torsional barriers of the o - and p -methyl groups were determined to be 227.039(51) cm −1 and 3.23(40) cm −1 , respectively. The V 3 barrier observed for the p -methyl group is lower than in any other para -methyl substituted toluene derivatives with coupled internal rotations, becoming the lowest value ever observed to date. The barrier to internal rotation of the o -methyl group next to a fluorine atom is consistently around 220 cm −1 , as confirmed by comparing it to barriers observed in other toluene derivatives. The experimental rotational constants were compared to those obtained by quantum chemical calculations. Analysis of the 2,4-dimethylfluorobenzene microwave spectrum revealed the lowest potential barrier hindering a methyl internal rotor ever observed for dimethylsubstituted toluene derivatives to date.