Semiclassical Dynamics on Machine-Learned Coupled Multireference Potential Energy Surfaces: Application to the Photodissociation of the Simplest Criegee Intermediate

Abstract

Determination of high-dimensional potential energy surfaces (PESs) and nonadiabatic couplings have always been quite challenging. To this end, machine learning (ML) models, trained with a finite set of ab initio data, allow accurate prediction of such properties. To express the PESs in terms of atomic contributions is the cornerstone of any ML based technique because it can be easily scaled to large systems. In this work, we have constructed high fidelity PESs and nonadiabatic coupling terms at the CASSCF level of ab initio data using a machine learning technique, namely, kernel-ridge regression. Additional MRCI-level calculations were carried out to assess the quality of the PESs. We use these machine-learned PESs and nonadiabatic couplings to simulate excited-state molecular dynamics based on Tully�s fewest-switches surface hopping method (FSSH). FSSH is a semiclassical method in which nuclei move on the PESs due to the electrons according to the laws of classical mechanics. Nonadiabatic effects are taken into account in terms of transitions between PESs. We apply this scheme to study the O-O photodissociation of the simplest Criegee intermediate (CH2OO). The FSSH trajectories were initiated on the lowest optically bright singlet excited state (S2) and propagated along the three most important internal coordinates, namely, O-O and C-O bond distances and the COO bond angle. Some of the trajectories end up on energetically lower PESs as a result of radiationless transfer through conical intersections. All of the trajectories lead to the dissociation of the O-O bond due to the dissociative nature of the excited PESs through one of the two dissociative channels. The simulation reveals that there is about 88.4% probability of dissociation through the lower channel leading to the H2CO (X1A1) and O (1D) products, whereas there is only 11.6% probability of dissociation through the upper channel leading to H2CO (a3A?) and O (3P) products. � 2023 American Chemical Society.