Intramolecular vibrational energy redistribution in DCO (2A′): Classical-quantum correspondence, dynamical assignments of highly excited states, and phase space transport

Abstract

Intramolecular dynamics of highly excited DCO (²A′) is studied from a classical-quantum correspondence perspective using the effective spectroscopic Hamiltonian proposed recently by Tröllsch and Temps (Z. Phys. Chem., 2001, 215, 207). This work focuses on the polyads P = 3 and P = 4 corresponding to excitation energies E_v ≈ 5100 cm⁻¹ and 7000 cm⁻¹, respectively. The majority of states belonging to these polyads are dynamically assigned, despite extensive stochasticity in the classical phase space, using the recently proposed technique of level velocities. A wavelet based time–frequency analysis is used to reveal the nature of phase space transport and the relevant dynamical bottlenecks. The local frequency analysis clearly illustrates the existence of mode-specific IVR dynamics, i.e., differing nature of the IVR dynamics ensuing from CO stretch and the DCO bend bright states. In addition, the role of the weak Fermi resonance involving the CO stretch and DCO bend modes is investigated. A key feature of the present work is that the techniques utilized for the analysis, i.e. parametric variations and local frequency analysis, are not limited by the dimensionality of the system. This study, thus, explores the potential for understanding IVR in larger molecules from both time domain and frequency domain perspectives.