Skeletal Torsion Tunneling and Methyl Internal Rotation: The Coupled Large Amplitude Motions in Phenyl Acetate

The rotational spectrum of phenyl acetate, CH₃COOC₆H₅, is measured using a free jet absorption millimeter-wave spectrometer in the range from 60 to 78 GHz and two pulsed jet Fourier transform microwave spectrometers covering a total frequency range from 2 to 26.5 GHz. The features of two large amplitude motions, the methyl group internal rotation and the skeletal torsion of the CH₃COO group with respect to the phenyl ring C₆H₅ (tilted at about 70°), characterize the spectrum. The vibrational ground state is split into four widely spaced sublevels, labeled as A0, E0, A1, and E1, each of them with its set of rotational transitions and with additional interstate transitions. A global fit of the line frequencies of the four sublevels leads to the determination of 51 spectroscopic parameters, including the ΔE_A0/A1 and ΔE_E0/E1 vibrational splittings of ~36.4 and ~33.5 GHz, respectively. The V₃ barrier to methyl internal rotation (~136 cm⁻¹) and the skeletal torsion B₂ barrier to the orthogonality of the two planes (~68 cm⁻¹) are deduced.