A direct dynamics study of the exotic photochemistry of the simplest Criegee intermediate, CH ₂OO

Abstract

A seven-state multidimensional CASPT2 trajectory surface hopping study of the simplest Criegee intermediate reveals asymptotic coupling between dissociating fragments.

Abstract

Criegee intermediates are amongst the most fascinating molecules in modern-day chemistry. They are highly reactive intermediates that find vital roles that range from atmospheric chemistry to organic synthesis. Their excited state chemistry is exotic and complicated, and a myriad of electronic states can contribute to their photodissociation dynamics. This article reports a multi-state direct dynamics (full-dimensional) study of the photoinduced fragmentation of the simplest Criegee intermediate, CH ₂OO, using state-of-the-art MS-CASPT2 trajectory surface hopping. Following vertical excitation to the strongly absorbing S ₂( ¹ππ*) state, internal conversion, and thus changes in the electronic state character of the separating O + CH ₂O fragments, is observed between parent electronic states at separations that, traditionally, might be viewed as the classically asymptotic region of the potential energy surface. We suggest that such long-range internal conversion may account for the unusual and non-intuitive total kinetic energy distribution in the O( ¹D) + CH ₂O(S ₀) products observed following photoexcitation of CH ₂OO. The present results also reveal the interplay between seven singlet electronic states and dissociation to yield the experimentally observed O( ¹D) + CH ₂O(S ₀) and O( ³P) + CH ₂O(T ₁) products. The former (singlet) products are favored, with a branching ratio of ca. 80%, quantifying the hitherto unknown product branching ratios observed in velocity map imaging experiments. To the best of our knowledge, such long-range internal conversions that lead to changes in the electronic state character of the fragment pairs originating from a common parent – at classically asymptotic separations – have not been recognized hitherto in the case of a molecular photodissociation.