Sub-Doppler Infrared Spectra and Torsion-Rotation Energy Manifold of Methanol in the CH-Stretch Fundamental Region.

The infrared spectrum of jet-cooled methanol in the CH-stretch fundamental region has been investigated by two sub-Doppler laser techniques: optothermally detected molecular-beam electric resonance and direct-absorption slit-jet spectroscopy. With the aid of microwave-infrared double resonance and ground state combination differences, 27 subbands in the frequency range 2967 to 3027 cm-1 have been assigned to the nu2 fundamental. Perturbation systems in the K' = 0 E, -1 E, and -2 E symmetry subbands have been analyzed to yield matrix elements of 0.013, 0.041, and 0.75 cm-1, respectively. The A-E torsional tunneling splitting for J = 0 of the nu2 vibration of -3.26 cm-1 is of opposite sign and a factor of three smaller in magnitude than the ground state value of +9.12 cm-1. Copyright 1997 Academic Press. Copyright 1997Academic Press