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In nonadiabatic photoreactions in solution, the geometry at the decay region from the excited to the ground state is decisive for the outcome of the reaction. From a mechanistic point of view, this "reactive structun", is., the structure of the conical intersection accessible on the excited state of a singlet photoreaction or the region of geometries favorable for intersystem crossing in a triplet photoreaction, plays a similar role as the transition state in a thermal reaction. Consequences for the selectivity of singlet and triplet photoreactions are discussed.

Theoretical models for the selectivity of organic singlet and triplet photoreactions