Assigning vibrational polyads using relative equilibria: application to ozone.

Abstract

We demonstrate how relative equilibria of a vibrating molecule, which are families of principal periodic orbits otherwise known as nonlinear normal modes, can be used to describe the global polyad structure of vibrational energy levels. The classical action integral n(E) computed along these orbits at different energies E corresponds to the polyad quantum number n so that the energy En of different relative equilibria describes the splitting of n-polyads. Further information on the internal polyad structure can be driven from the stability analysis of relative equilibria. We use the ozone molecule as a concrete example where n-polyads or "hyperpolyads" should be distinguished from the well-known polyads of the 1:1 stretching mode resonance; the stretching polyads are structural elements of hyperpolyads. We give dynamical interpretation of the relation between relative equilibria and n-polyads based on the normal form reduction in the limit of small vibrations near the equilibrium.