MEASURING THE RATE OF ENERGY FLOW ACROSS THE SEPARATRIX USING A MOLECULAR GYROSCOPE
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Abstract
The dynamics of methyl group rotation qualitatively change when the energy in the torsional coordinate exceeds the barrier to internal rotation. This problem is similar to the simple pendulum. Below the barrier, the motion of the methyl top is torsional oscillation while above the barrier the top undergoes full rotation about its symmetry axis. In a phase space description, a separatrix divides the phase space between these two characteristic types of motion. Recent nonlinear dynamics studies of isomerization reactions indicate that there is a barrier to energy flow across the separatrix that leads to violations of transition state theory rate predictions. We apply our technique of dynamical rotational spectroscopy to measure the energy flow rate across the separatrix for Z-pentenyne at a total energy of
Description
Author Institution: University of Virginia; Department of Chemistry, University of Virginia