Onset of quantum chaos in molecular systems and the zeros of the Husimi function.

The distribution of zeros of the Husimi function has proven a useful tool in the characterization of regular and chaotic quantum states of dynamical systems. In a previous paper [Phys. Rev. E 82, 026201 (2010)], we showed how the quantum transition from order to chaos in three different molecular systems (LiCN, HCN, and HO(2)) can be understood by means of the correlation diagram of eigenenergies versus the Planck's constant. An order-chaos frontier of scars (eigenstates localized over unstable and stable complementary, in the sense of the Poincaré-Birkhoff theorem, periodic orbits) was observed. In this paper, we show how the distribution of zeros of the Husimi function can be related to the onset of chaos in these molecular systems, showing a very interesting feature at the frontier of scars; namely, some zeros of the Husimi function localize over the stable and unstable fixed points corresponding to the two complementary periodic orbits, this representing the quantum equivalent to the Poincaré-Birkhoff theorem.

Scars at the edge of the transition from order to chaos in the isomerizing molecular systems LiNC-LiCN and HCN-HNC, and HO2.

Correlation diagrams of energy levels using ℏ as the varying parameter have proven very useful in the characterization of quantum vibrational dynamics of small polyatomic molecules, specially in relation to the transition from order to chaos. In this paper, we present calculations of such correlation diagrams for three molecular systems with very different characteristics, which can be traced down to the topology of their potential energy surfaces. By studying the broad avoided crossings existing in the diagrams, we show that the transition from regular to irregular states always corresponds to a frontier formed by scarred states.