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DAVID RUEDA, O. V. BOYARKIN AND T. R. RIZZO, INSTITUT DE CHIMIE PHYSIQUE MOLECULAIRE, EPFL, CH - 1015 LAUSANNE; ANDREI CHIROKOLAVA, INDRANATH MUKHOPADHYAY AND DAVID S PERRY, DEPARTMENT OF CHEMISTRY, UNIVERSITY OF AKRON, AKRON, OHIO 44325.
Overtone spectra of jet-cooled methanol have been recorded from 5,000 to 14,000 cm-1 using Infrared Laser Assisted Photofragment Spectroscopy (IRLAPS) for the detection of the vibrationally excited molecules.
In addition to the OH stretch overtones (n
1), the major components of the spectra are the overtones of the CH stretch (up to 5
CH) as well as combinations of the OH stretch with the CO stretch (n
1+
8), the COH bend (n
1+
6), and both (n
1+
6+
8). These data, together with photoacoustic data [1] up to 18,250 cm-1 and previously reported IRLAPS data [2] up to 22,166 cm-1, have been fit to an anharmonic Hamiltonian. In this Hamiltonian, the CH stretch vibrations are treated as a pair of local modes,
a and
b, for vCH = 3 and higher. The other modes are treated as the usual normal vibrations.
[1] H.L. Fang, D.M. Meister, R.L. Swofford, J. Phys. Chem. 88, 405-409 (1984).
[2] O.V. Boyarkin, L. Lubich, R.D.F. Settle, D.S. Perry, T.R. Rizzo, J. Chem. Phys. 107, 8409-8422 (1997).