State-Resolved Intramolecular Dynamics in Highly Excited HOCl

摘要

The features and mechanisms of intramolecular energy redistribution (IVR) and state mixing of HOCl at chemically significant energies have been investigated using intra-cavity laser absorption spectroscopy (ICLAS). These studies revealed that for the observed vibrational states up to about 75/100 of the dissociation energy E_0 Both strong and weak interactions (Fermi-type, Coriolis)exist but producing only localized perturbations in the Spectra. The 5 v_1 band, however, at about 85/100 of the dissociation threshold E_0 (O-Cl bond) has been found to Be globally and strongly mixed with the 4 v_1 + 2 v_2 + v_3 zero-order vibrational state, and both states appeared in Turn coupled to other background states by additional (weaker) interactions.