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, wheth

SUBMITTER: Manikandan P 

PROVIDER: S-EPMC4209979 | biostudies-literature | 2014 Oct

REPOSITORIES: biostudies-literature