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Register a new userRoaming dynamics in Ketene isomerization
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A reduced two dimensional model is used to study Ketene isomerization reaction. In light of recent results by Ulusoy textit{et al.} [J. Phys. Chem. A {bf 117}, 7553 (2013)], the present work focuses on the generalization of the roaming mechanism to the Ketene isomerization reaction by applying our phase space approach previously used to elucidate the roaming phenomenon in ion-molecule reactions. Roaming is again found be associated with the trapping of trajectories in a phase space region between two dividing surfaces; trajectories are classified as reactive or nonreactive, and are further naturally classified as direct or non-direct (roaming). The latter long-lived trajectories are trapped in the region of non-linear mechanical resonances, which in turn define alternative reaction pathways in phase space. It is demonstrated that resonances associated with periodic orbits provide a dynamical explanation of the quantum mechanical resonances found in the isomerization rate constant calculations by Gezelter and Miller [J. Chem. Phys. {bf 103}, 7868-7876 (1995)]. Evidence of the trapping of trajectories by `sticky resonant periodic orbits is provided by plotting Poincare surfaces of section, and a gap time analysis is carried out in order to investigate the statistical assumption inherent in transition state theory for Ketene isomerization.
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We explore both classical and quantum dynamics of a model potential exhibiting a caldera: that is, a shallow potential well with two pairs of symmetry related index one saddles associated with entrance/exit channels. Classical trajectory simulations at several different energies confirm the existence of the `dynamical matching phenomenon originally proposed by Carpenter, where the momentum direction associated with an incoming trajectory initiated at a high energy saddle point determines to a considerable extent the outcome of the reaction (passage through the diametrically opposing exit channel). By studying a `stretched version of the caldera model, we have uncovered a generalized dynamical matching: bundles of trajectories can reflect off a hard potential wall so as to end up exiting predominantly through the transition state opposite the reflection point. We also investigate the effects of dissipation on the classical dynamics. In addition to classical trajectory studies, we examine the dynamics of quantum wave packets on the caldera potential (stretched and unstretched). These computations reveal a quantum mechanical analogue of the `dynamical matching phenomenon, where the initial expectation value of the momentum direction for the wave packet determines the exit channel through which most of the probability density passes to product.
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