Theoretical studies of the potential surface and vibrational spectroscopy of CH3OH and its deuterated analogs.
A potential-energy force field for methanol is calculated at the coupled-cluster singles doubles and noniterative triples correction level using the correlation-consistent polarized valence triple zeta basis set. The force field describes the coupled molecular vibrations, including the cubic and quartic anharmonicites, as a function of the torsional coordinate. The resulting molecular eigenstates are calculated using a combination of perturbative and variation calculations following the approach of Castillo-Chará and Sibert [J. Chem. Phys. 119, 11671 (2003)]. The energies, including torsional tunneling splittings, are compared with available spectroscopic data for all the fundamentals. Excellent agreement is found. Varying the torsional mass, correlation plots are constructed in order to elucidate the complex role of torsion-vibration coupling.
Sibert
Edwin L
EL
Department of Chemistry and Theoretical Chemistry Institute, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA. sibert@chem.wisc.edu
Castillo-Chará
Jairo
J