Semiclassical calculation of bound states in a multidimensional system for nearly 1:1 degenerate systems

Abstract

The method is devised to calculate eigenvalues semiclassically for an anharmonic system whose two unperturbed modes are 1:1 degenerate, by introducing a curvilinear Poincaré surface of section. The results are in reasonable agreement with the quantum ones. The classical trajectories also frequently show a large energy exchange among the two unperturbed normal modes. Implications for Slater's theory of unimolecular reactions, which neglects this effect, and for "quantum ergodicity" are described.