Abstract

Recent theoretical work done by our group on intramolecular vibrational energy redistribution (IVR) has shown that significant deviations from traditional Golden Rule behavior, such as nonexponential decays and linear dependence of the IVR rate on coupling strength, are the norm rather than the exception, particularly in vibrations involving heavy atoms. These departures arise as the result of an IVR mechanism that depends on a sequential flow of energy through chains of dark states that can be loosely grouped into tiers, as opposed to the direct one step picture presented by the Golden Rule, The most striking prediction of our mode] is that, as a result of the relatively small subset of gateway states responsible for the initial amplitude flow out of the vibration of interest, the electric fields required to dramatically reduce the IVR rate are relatively simple, and can be produced in the laboratory with currently available technology.

© 1997 Optical Society of America