A simple yet realistic model Hamiltonian which describes the essence of many aspects of the interaction of vibrational modes in polyatomics is discussed. The general form of the Hamiltonian is that of an intermediate case between the purely local mode and purely normal mode limits. Resonance interactions of the Fermi and Darlingndash;Dennison types are shown to be special cases. The classical limit of the Hamiltonian is used to provide a geometrical content for the model and to illustrate the lsquo;lsquo;phasehyphen;likersquo;rsquo; transition between local and collective (i.e., normal) mode behavior. Such transitions are evident as the coupling parameters in the Hamiltonian are changed and also for a given Hamiltonian as the energy is changed. Applications are provided to higher lying vibrational states of specific molecules (H2O, O3, SO2, C2H2, and C2D2).
展开▼