Bis-trifluoromethyl effect: doubled transitions in the rotational spectra of hexafluoroisobutene, (CF3)2C═CH2

J Phys Chem A. 2012 Aug 9;116(31):8169-75. doi: 10.1021/jp305812z. Epub 2012 Jul 31.

Abstract

Rotational spectra for hexafluoroisobutene, and its (13)C isotopologues, have been recorded between 8 and 16 GHz using a chirped pulse, Fourier transform microwave spectrometer. Notably, all spectra observed are doubled with separations between the doublets being between 1 and 60 MHz. We propose that the bis-trifluoromethyl groups of the target molecule are staggered in the equilibrium configuration, and that a novel, out-of-phase rotation through a F-CCC-F planar configuration with low barrier (<100 cm(-1)), leads to the observed doubled rotational spectra.