Development of Parallel On-the-Fly Crystal Algorithm for Global Exploration of Conical Intersection Seam Space

Abstract

Conical intersection (CI) seams are configuration spaces of a molecular system where two or more (spin) adiabatic electronic states are degenerate in energy. They play essential roles in photochemistry because nonradiative decays often occur near the minima of the seam, i.e., the minimum energy CIs (MECIs). Thus, it is important to explore the CI seams and discover the MECIs. Although various approaches exist for CI seam exploration, most of them are local in nature, requiring reasonable initial guesses of geometries and nuclear gradients during the search. Global search algorithms, on the other hand, are powerful because they can fully sample the configurational space and locate important MECIs missed by local algorithms. However, global algorithms are often computationally expensive for large systems due to their poor scalability with respect to the number of degrees of freedom. To overcome this challenge, we develop the parallel on-the-fly Crystal algorithm to globally explore the CI seam space, taking advantage of its superior scaling behavior. Specifically, Crystal is coupled with on-the-fly evaluations of the excited and ground state energies using multireference electronic structure methods. Meanwhile, the algorithm is parallelized to further boost its computational efficiency. The effectiveness of this new algorithm is tested for three types of molecular photoswitches of significant importance in material and biomedical sciences: photostatin (PST), stilbene, and butadiene. A rudimentary implementation of the algorithm is applied to PST and stilbene, resulting in the discovery of all previously identified MECIs and several new ones. A refined version of the algorithm, combined with a systematic clustering technique, is applied to butadiene, resulting in the identification of an unprecedented number of energetically accessible MECIs. The results demonstrate that the parallel on-the-fly Crystal algorithm is a powerful tool for automated global CI seam exploration.