Roaming dynamics in ketene isomerization

Abstract

A reduced two-dimensional model is used to study ketene isomerization reaction. In light of recent results by Ulusoy et al. (J Phys Chem A 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 nondirect (roaming). The latter long-lived trajectories are trapped in the region of nonlinear 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 103, 7868-7876, 1995). Evidence of the trapping of trajectories by 'sticky' resonant periodic orbits is provided by plotting Poincaré 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. © 2014 The Author(s).