Discovery of conical intersection mediated photochemistry with growing string methods

Abstract

Conical intersections (CIs) are important features of photochemistry that determine yields and selectivity. Traditional CI optimizers require significant human effort and chemical intuition, which typically restricts searching to only a small region of the CI space. Herein, a systematic approach utilizing the growing string method is introduced to locate multiple CIs. Unintuitive MECI are found using driving coordinates that can be generated using a combinatorial search, and subsequent optimization allows reaction pathways, transition states, products, and seam-space pathways to be located. These capabilities are demonstrated by application to two prototypical photoisomerization reactions and the dimerization of butadiene. In total, many reaction pathways were uncovered, including the elusive stilbene hula-twist mechanism, and a previously unidentified product in butadiene dimerization. Overall, these results suggest that growing string methods provide a predictive strategy for exploring photochemistry.