Quantum Dynamics of Oblique Vibrational States in the Hénon-Heiles System.

In this paper, we study the quantum time evolution of oblique nonstationary vibrational states in a Henon-Heiles oscillator system with two dissociation channels, which models the stretching vibrational motions of triatomic molecules. The oblique nonstationary states we are interested in are the eigenfunctions of the anharmonic zero-order Hamiltonian operator resulting from the transformation to oblique coordinates, which are defined as those coming from nonorthogonal coordinate rotations that express the matrix representation of the second-order Hamiltonian in a block diagonal form characterized by the polyadic quantum number n = n(1) + n(2). The survival probabilities calculated show that the oblique nonstationary states evolve within their polyadic group with a high degree of coherence up to the dissociation limits on the short time scale. The degree of coherence is certainly much higher than that exhibited by the local nonstationary states extracted from the conventional orthogonal rotation of the original normal coordinates. We also show that energy exchange between the oblique vibrational modes occurs in a much more regular way than the exchange between the local modes.