Comparing the Excited State Dynamics of CH2OO, the Simplest Criegee Intermediate, Following Vertical versus Adiabatic Excitation.

Abstract

Ab initio molecular dynamics studies of CH2OO molecules following excitation to the minimum-energy geometry of the strongly absorbing S2 (1ππ*) state reveal a much richer range of behaviors than just the prompt O-O bond fission, with unity quantum yield and retention of overall planarity, identified in previous vertical excitation studies from the ground (S0) state. Trajectories propagated for 100 fs from the minimum-energy region of the S2 state show a high surface hopping (nonadiabatic coupling) probability between the near-degenerate S2 and S1 (1nπ*) states at geometries close to the S2 minimum, which enables population transfer to the optically dark S1 state. Greater than 80% of the excited population undergoes O-O bond fission on the S2 or S1 potential energy surfaces (PESs) within the analysis period, mostly from nonplanar geometries wherein the CH2 moiety is twisted relative to the COO plane. Trajectory analysis also reveals recurrences in the O-O stretch coordinate, consistent with the resonance structure observed at the red end of the parent S2-S0 absorption spectrum, and a small propensity for out-of-plane motion after nonadiabatic coupling to the S1 PES that enables access to a conical intersection between the S1 and S0 states and cyclization to dioxirane products.