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Intramolecular vibrational energy redistribution/relaxation (IVR) is paramount to understanding the dynamics and mechanism of chemical reactions. In particular, the competition between IVR and reaction timescales decides as to whether or not we can use statistical reaction rate theories and bypass the need to characterize and quantify the complex intramolecular dynamics. Nevertheless, determining the relevant IVR pathways in molecules with several degrees of freedom has proved to be a formidable challenge. In part, and notwithstanding the intrinsically quantum nature of molecules, the challenge has to do with our incomplete understanding of the classical IVR dynamics on the Arnold web i.e., the network of nonlinear resonances (analogs of Fermi resonances) involving various vibrational modes of the molecule. Recent work, inspired by earlier studies, indicate that certain features of the resonance network can play an important role in regulating the IVR in the system. Specifically, the vicinity of junctions of two or more independent resonances seem to be crucial to the IVR dynamics. In this talk I discuss the recent results, some plausible conjectures, and highlight issues that are still wide open. |