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Zusammenfassung:
The vibrational motion of highly excited molecules is discussed in terms of exact quantum and classical mechanics calculations, employing global potential energy surfaces, as well as in terms of a spectroscopic Hamiltonian and its semiclassical limit. The main focus is saddle-node bifurcations and their influence on the spectrum. The general features are illustrated by three examples, which despite their quite different intramolecular motions have several aspects in common: HCP, HOCl, and HOBr. In all three cases a 1:2 Fermi resonance is the ultimate cause of the complications observed in the spectra.
