Vibrational energy flow in highly excited molecules: Role of intramolecular vibrational redistribution

A pedagogical overview of intramolecular vibrational redistribution (IVR) phenomena in vibrationally excited molecules is presented. In the interest of focus and simplicity, the topics covered deal primarily with IVR in the ground electronic state, relying on examples from the literature to illustrate key points. The experimental topics discussed attempt to sample systematically three different energy regimes on the full potential surface corresponding to (i) ''low'', e.g., moderate- to high-resolution vibrational spectroscopies, (ii) ''intermediate'', e.g., stimulated emission pumping and high overtone spectroscopies, and (iii) ''high'', e.g., photofragment/ predissociation dynamical spectroscopies. The interplay between experiment and theory is highlighted here because it has facilitated enormous advances in the field over the past decade.