Anharmonic force field for methanol |
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| Authors: | ANDREA MIANI VESA HÄNNINEN MATTHIAS HORN LAURI HALONEN |
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| Institution: | 1. Laboratory of Physical Chemistry , University of Helsinki , P.O. Box 55 (A. I. Virtasen aukio 1), FIN-00014, Finland;2. Laboratory of Physical Chemistry , University of Helsinki , P.O. Box 55 (A. I. Virtasen aukio 1), FIN-00014, Finland;3. JILA, University of Colorado , Campus Box 440, Boulder, Colorado, 80309-0440, USA |
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| Abstract: | An ab initio quartic anharmonic force field for methanol has been calculated at the equilibrium position using the CCSD(T) method for the structure and the harmonic potential energy surface, and the MP4(SDQ) method for the anharmonic part of the surface. A triple zeta basis set was employed with symmetrized curvilinear internal valence coordinates in all calculations. The internal coordinate force field constants have been transformed into force constants in the dimensionless normal coordinate representation for various isotopomers. Vibrational term values for CH3OH, CH3OD, CD3OH, and CD3OD have been obtained using second order perturbation theory. Particular care has been devoted to the inclusion of Fermi resonance interactions between different vibrational states. A good accuracy has been achieved in the calculation of the fundamentals for all the isotopomers, the mean absolute error being 5.8 cm?1. |
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