We present a novel approach to the control of selectivity of reaction products. The central idea is that in a two‐photon or multiphoton process that is resonant with an excited electronic state, the resonant excited state potential energy surface can be used to assist chemistry on the ground state potential energy surface. By controlling the delay between a pair of ultrashort (femtosecond) laser pulses, it is possible to control the propagation time on the excited state potential energy surface. Different propagation times, in turn, can be used to generate different chemical products. There are many cases for which selectivity of product formation should be possible using this scheme. We illustrate the methodology with numerical application to a variety of model two degree of freedom systems with two inequivalent exit channels. Branching ratios obtained using a swarm of classical trajectories are in good qualitative agreement with full quantum mechanical calculations.

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