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Intertorsional Interactions Revealing Absolute Configurations: The V 6 Internal Rotation Heavy‐Top Case of Benzotrifluoride
Author(s) -
Ilyushin Vadim V.,
Favero Laura B.,
Caminati Walther,
Grabow JensUwe
Publication year - 2010
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201000223
Subject(s) - internal rotation , fourier transform , torsion (gastropod) , rotation (mathematics) , microwave , chemistry , spectral line , rotation around a fixed axis , physics , atomic physics , geometry , classical mechanics , mathematics , quantum mechanics , engineering , mechanical engineering , medicine , surgery
The microwave spectroscopic signatures of multiple torsional states of the CF 3 internal rotation in benzotrifluoride (α,α,α‐trifluorotoluene) are reported. Individual rotational transitions are observed in a total of eight different torsional states, a quite challenging task for heavy tops even with Fourier transform microwave techniques. Accidental mixings of m =0 and m =3 torsional states as well as m =1 and m =2 torsional states, which can complicate the assignment of the spectra severely, are observed. These accidental mixings are probably systematic for molecules with heavy tops exhibiting an almost free internal rotation, and give an opportunity to determine the sign in the (1/2) V 6 (1±cos6 τ ) potential function hindering internal rotation and in consequence the orientation of the CF 3 top versus C 6 H 5 frame. A recently developed torsion–rotation program reproduces all line positions within an experimental accuracy of about 2.0 kHz. The V 6 barrier is determined to be 3.229949(32) cm −1 . The corresponding torsional spacings are determined with the seven‐digit accuracy underlying the supersonic‐jet Fourier transform microwave technique.