Analyzing intramolecular vibrational energy redistribution via the overlap intensity-level velocity correlator

Abstract

Numerous experimental and theoretical studies have established that intramolecular vibrational energy redistribution (IVR) in isolated molecules has a heirarchical tier structure. The tier structure implies strong correlations between the energy level motions of a quantum system and its intensity-weighted spectrum. A measure, which explicitly accounts for this correaltion, was first introduced by one of us as a sensitive probe of phase space localization. It correlates eigenlevel velocities with the overlap intensities between the eigenstates and some localized state of interest. A semiclassical theory for the correlation is developed for systems that are classically integrable and complements earlier work focusing exclusively on the chaotic case. Application to a model two dimensional effective spectroscopic Hamiltonian shows that the correlation measure can provide information about the terms in the molecular Hamiltonian which play an important role in an energy range of interest and the character of the dynamics. Moreover, the correlation function is capable of highlighting relevant phase space structures including the local resonance features associated with a specific bright state. In addition to being ideally suited for multidimensional systems with a large density of states, the measure can also be used to gain insights into the phase space transport and localization. It is argued that the overlap intensity-level velocity correlation function provides a novel way of studying vibrational energy redistribution in isolated molecules. The correlation function is ideally suited to analyzing the parametric spectra of molecules in external fields.