Rich Athermal Ground‐State Chemistry Triggered by Dynamics through a Conical Intersection

A fundamental tenet of statistical rate theories (such
as transition state theory and RRKM) is the rapidity of
vibrational relaxation. Excited-state reactions happen quite
quickly (sub-picosecond) and thus can exhibit nonstatistical
behavior. However, it is often thought that any diversity of
photoproducts results from different conical intersections
connecting the excited and ground electronic states. It is also
conceivable that the large energy of the photon, which is
converted to vibrational energy after electronic transitions
could lead to athermal hot ground state reactions and that these
might be responsible for the diversity of photoproducts. Here
we show that this is the case for sulfines, where a single conical
intersection is implicated in the electronic transition but the
excited state reaction leads to nine different products within less
than a picosecond.