Ultrafast Ring-Opening Reaction of 1,3-Cyclohexadiene: Identification of Nonadiabatic Pathway via Doubly Excited State

Abstract

The photoinduced ring-opening reaction of 1,3-cyclohexadiene (CHD) to produce 1,3,5-hexatriene (HT) plays an essential role in the photobiological synthesis of vitamin D₃ in the skin. This reaction follows the Woodward-Hoffmann rule, and C₅-C₆ bond rupture via an electronically excited state occurs with conrotatory motion of the end CH₂ groups. However, it is noted that the photoexcited S₁(π,π*) state of CHD is not electronically correlated with the ground state of HT, and the reaction must proceed via nonadiabatic transitions. In the present study, we have clearly observed the nonadiabatic reaction pathway via the doubly excited state of CHD using ultrafast extreme UV photoelectron spectroscopy. The results indicate that the reaction occurs in only 68 fs and creates product vibrational coherence. Extensive computational simulations support the interpretation of experimental results and provide further insights into the electronic dynamics in this paradigmatic electrocyclic ring-opening reaction.