Paper detail

The Phase Space Mechanism for Selectivity in a Symmetric Potential Energy Surface with a Post-Transition-State Bifurcation

Chemical selectivity is a phenomenon displayed by potential energy surfaces (PES) that is relevant for many organic chemical reactions whose PES feature a valley-ridge inflection point (VRI) in the region between two sequential index-1 saddles. In this letter we describe the underlying dynamical phase space mechanism that qualitatively determines the product distributions resulting from bifurcating reaction pathways. We show that selectivity is a consequence of the heteroclinic and homoclinic connections established between the invariant manifolds of the families of unstable periodic orbits (UPOs) present in the system. The geometry of the homoclinic and heteroclininc connections is determined using the technique of Lagrangian descriptors, a trajectory-based scalar technique with the capability of unveiling the geometrical template of phase space structures that characterizes transport.