The vibrational dynamics of HOCl and HOBr between bending and OCl/OBr stretching coordinates with anharmonicity and Fermi coupling is studied with the classical dynamical potential approach. The quantal vibrational dynamics is mostly mapped out by the classical nonlinear variables such as fixed points, except for the state energies, which are quantized. This approach is global in the sense that the focus is on a set of levels instead of individual ones. The dynamics of HOBr is demonstrated to be less complicated. The localized modes along the OCl/OBr stretching coordinates are also shown to have O-Br bonds more prone to dissociation.
The highly excited vibrational levels of HCO in the electronic ground state,X 1A,are employed to determine the coefficients of an algebraic Hamiltonian,by which the dynamical potential is derived and shown to be very useful for interpreting the intramolecular vibrational relaxation(IVR) which operates via the HCO bending motion.The IVR inhibits the dissociation of H atom and enhances the stochastic degree of dynamical character.This approach is from a global viewpoint on a series of levels classified by the polyad number which is a constant of motion in a certain dynamical domain.In this way,the seemingly complicated level structure shows very regular picture,dynamically.
This paper studies the vibrational nonlinear dynamics of nitrous oxide with Fermi coupling between the symmetric stretching and bending coordinates by classical dynamical potential approach.This is a global approach in the sense that the overall dynamics is evidenced by the classical nonlinear variables such as the fixed points and the focus are on a set of levels instead of individual ones.The dynamics of nitrous oxide is demonstrated to be not so much dependent on the excitation energy.Moreover,the localized bending mode is shown to be ubiquitous in all the energy range studied.
