The influence of a pitchfork bifurcation of the critical points of a symmetric caldera potential energy surface on dynamical matching

Many organic chemical reactions are governed by potential energy surfaces that have a region with the topographical features of a caldera. If the caldera has a symmetry then trajectories transiting the caldera region are observed to exhibit a phenomenon that is referred to as dynamical matching. Dynamical matching is a constraint that restricts the way in which a trajectory can exit the caldera based solely on how it enters the caldera. In this paper we show that bifurcations of the critical points of the caldera potential energy surface can destroy dynamical matching even when the symmetry of the caldera is not affected by the bifurcation.