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Journal of Physical Chemistry A, Vol.114, No.25, 6913-6916, 2010
Rotational Spectrum, Tunneling Motions, and Potential Barriers of Benzyl Alcohol
The rotational spectra of benzyl alcohol and of its OD isotopologue have been assigned and measured in a supersonic expansion, either with pulsed-jet Fourier transform microwave or free jet absorption millimeter wave spectroscopy. The spectrum is consistent with a gauche conformation of the oxygen atom, characterized by a theta (OC7-C1C2) dihedral angle of approximately 55 degrees. Such a configuration is 4-fold degenerate, corresponding to minima with theta approximate to +/- 60 degrees, +/- 120 degrees. The four equivalent minima are separated by two kinds of barrier, corresponding to theta = +/- 90 degrees, and 0 or 180 degrees. Only the theta = +/- 90 degrees barriers are low enough to generate a tunneling splitting, which has been measured in a spectrum strongly perturbed by tunneling interactions. The observed splittings diminish considerably upon deuterium substitution. The tunneling splittings are consistent with a barrier about 280 cm(-1) and high level ab initio calculations predicting a 320 cm(-1) barrier.