A model for impulsive mode–mode energy transfer in highly vibrationally excited molecules.

The classical dynamics of mode–mode vibrational energy transfer are investigated for a coupled Morse oscillator system by explicitly integrating Hamiltonian’s equations in action–angle coordinates. This method permit the identification of specific oscillator phase relationships which dictate the extent and timing of large-scale, nonperiodic energy transfer; we term this ‘‘impulsive energy transfer.’’ In previous classical trajectory studies, such impulsive events have been related to the dynamics of isomerization immediately prior to reaction. A qualitative understanding of the required phase relationships for impulsive energy transfer is gained via the Chirikov hindered rotor analysis, usually applied to resonant energy flow. The implications of the model are illustrated in a three mode isomerization system. [ABSTRACT FROM AUTHOR]