  Statistical models provide a powerful and useful class of approximations for
calculating reaction rates by bypassing the need for detailed, and often
difficult, dynamical considerations. Such approaches invariably invoke specific
assumptions about the extent of intramolecular vibrational energy flow in the
system. However, the nature of the transition to the statistical regime as a
function of the molecular parameters is far from being completely understood.
Here, we use tools from nonlinear dynamics to study the transition to
statisticality in a model unimolecular reaction by explicitly visulaizing the
high dimensional classical phase space. We identify generic features in the
phase space involving the intersection of two or more independent anharmonic
resonances and show that the presence of correlated, but chaotic,
intramolecular dynamics near such junctions leads to nonstatisticality.
Interestingly, akin to the stability of asteroids in the Solar System,
molecules can stay protected from dissociation at the junctions for several
picoseconds due to the phenomenon of stable chaos.
