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Chemical selectivity, as quantified by a branching ratio, is a phenomenonrelevant for many organic chemical reactions. It may be exhibited on apotential energy surface that features a valley-ridge inflection point in theregion between two sequential index-1 saddles, with one saddle having higherenergy than the other. Reaction occurs when a trajectory crosses the region ofthe higher energy saddle (the entrance channel) and approaches the lower energysaddle. On both sides of the lower energy saddle, there are two wells and thequestion we address in this work is that, given an initial ensemble oftrajectories, what is the relative fraction of trajectories that enter eachwell. For a symmetric PES this fraction is 1:1. We consider a symmetric PESsubjected to a time-periodic forcing characterized by an amplitude, frequency,and phase. In this letter we analyse how the branching ratio depends on thesethree parameters.

Tuning the Branching Ratio in a Symmetric Potential Energy Surface with a Post-Transition State Bifurcation using External Time Dependence