Quantum and classical vibrational chaos in floppy molecules

Abstract

Classical and quantum mechanical calculations on the vibrational motions of LiCN using a realistic potential are presented. These, together with recent results for KCN, are analyzed using indicators that have been proposed for identifying quantum chaos. These are nodal structure, dominant coefficient, overlapping avoided crossings, second differences, and spectral distribution. We find an early onset of chaos in LiCN and KCN with good agreement between the indicators. Localized quasiperiodic trajectories and regular states are found well into the chaotic region for both isomers of LiCN. LiCN is a weakly coupled system in contrast to strongly coupled KCN. The utility of the indicators is discussed in the light of these results. The link between floppy molecules and chaos suggests that floppy systems are suitable for the experimental investigation of vibrational chaos.