Abstract
Recent experimental and theoretical methods allowed the efficient investigation of highly excited rovibrational states of molecular systems. At these levels of excitation the correspondence principle holds, and then classical mechanics can provide intuitive views of the involved processes. In this respect, we have recently shown that for completely hyperbolic systems, homoclinic motions, which are known to organize the classical chaotic region in Hamiltonian systems, imprint a clear signature in the corresponding highly excited quantum spectra. In this Communication we show that this result also holds in mixed systems, by considering an application to the floppy LiNCLiCN molecular system.
Highlights
The development of modern experimental techniques,1 such as stimulated emission pumping,2 or femtochemistry,3 greatly broadened the horizons of classical molecular spectroscopy
Molecular dynamics take place in the vicinity of Born–Oppenheimer potential energy surfacePESminima, where the motion corresponds to normal modes
At very high excitation energies, the interactions become too large and the picture based on normal mode states is no longer valid
Summary
The development of modern experimental techniques,1 such as stimulated emission pumping,2 or femtochemistry,3 greatly broadened the horizons of classical molecular spectroscopy. Molecular dynamics take place in the vicinity of Born–Oppenheimer potential energy surfacePESminima, where the motion corresponds to normal modes.
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