An entropic bottleneck, dynamical gating, and outward redistribution of roaming in a designed Chesnavich-type model

Abstract

Roaming reactions are organized not by potential-energy saddles but by transition states that are unstable invariant objects in phase space, periodic orbits in the two degrees of freedom studied here. To ask what controls roaming, we modify the Chesnavich model of a barrierless ion--molecule dissociation: its orientation-dependent angular hindrance is replaced by a transverse-stiffness ridge whose angular frequency peaks at an interior radius, and the classical dynamics are studied at a fixed energy just above the dissociation threshold. Comparing two ensembles that differ only in this angular interaction (same radial channel, energy, and inward initial conditions) isolates its effect. The ridge gates entry into the inner well, cutting inner capture from $57\%$ to $15\%$ and returning most of the incoming flux directly to reactants; it does not eliminate roaming but relocates it outward, suppressing it inside the ridge and switching it on farther out. The model retains analogues of the original model's three transition states (tight, free-rotor, and outer orbiting orbits), which we locate as unstable periodic orbits. The tight orbit spans a dividing surface that coincides, within numerical accuracy, with the variational minimum-flux surface, and it carries no barrier along the reaction coordinate: a deep entropic bottleneck placed at an interior radius by the stiffness maximum. Its entropic character is shared with the original model. Strength-matched monotone controls show that the gating tracks the hindrance strength at the bottleneck radius; what the interior maximum supplies is placement, concentrating that strength where it gates most effectively. The trajectories it admits roam nonstatistically, with nonexponential gap-time distributions: the entropic bottleneck governs how much is captured, not the dynamics that follow.