Abstract
The influence of the anisotropy of the potential of the CH chromophore in CHX 3 molecules is systematically investigated on the basis of ab initio results and model Hamiltonians for CD 3H and CHF 3. The coupling between levels with different vibrational angular momentum (quantum number l) introduced by typical potential anisotropies in a normal coordinate subspace for the CH chromophore is found to produce weak but possibly measurable changes in the overall structure of the overtone spectrum. The local C ∞v symmetry represented by the spectroscopic Fermi resonance Hamiltonian is shown to be retained as an approximate dynamical symmetry on the characteristic subpicosecond time scale of the chromophore dynamics. Predictions of the forbidden weak bands are presented and the time-dependent l non-conserving transitions are calculated explicitly.
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