title: Dynamical traps lead to the slowing down of intramolecular vibrational energy flow.
abstract: The phenomenon of intramolecular vibrational energy redistribution (IVR) is at the heart of chemical reaction dynamics. Statistical rate theories, assuming instantaneous IVR, predict exponential decay of the population with the properties of the transition state essentially determining the mechanism. However, there is growing evidence that IVR competes with the reaction timescales, resulting in deviations from the exponential rate law. Dynamics cannot be ignored in such cases for understanding the reaction mechanisms. Significant insights in this context have come from the state space model of IVR, which predicts power law behavior for the rates with the power law exponent, an effective state space dimensionality, being a measure of the nature and extent of the IVR dynamics. However, whether the effective IVR dimensionality can vary with time and whether the mechanism for the variation is of purely quantum or classical origins are issues that remain unresolved. Such multiple power law scalings can lead to surprising mode specificity in the system, even above the threshold for facile IVR. In this work, choosing the well-studied thiophosgene molecule as an example, we establish the anisotropic and anomalous nature of the quantum IVR dynamics and show that multiple power law scalings do manifest in the system. More importantly, we show that the mechanism of the observed multiple power law scaling has classical origins due to a combination of trapping near resonance junctions in the network of classical nonlinear resonances at short to intermediate times and the influence of weak higher-order resonances at relatively longer times.
authors.affiliation: Department of Chemistry, Indian Institute of Technology, Kanpur (U.P.) 208016, India.
authors.forename: Paranjothy
authors.initials: P
authors.lastname: Manikandan
authors.affiliation: Department of Chemistry, Indian Institute of Technology, Kanpur (U.P.) 208016, India srihari@iitk.ac.in.
authors.forename: Srihari
authors.initials: S
authors.lastname: Keshavamurthy
keywords: Arnold web; Fermi resonance; mode specificity; phase space; wavelets