We performed 1 picosecond (ps) non-adiabatic molecular dynamics (NAMD) simulations using the FSSH algorithm on 1 and 2, using Wigner-sampled initial conditions. For 1, 429 of the trajectories crossed to the S 0 after 1 ps (86%), while 71 (14%) remained on the S 1 . Of the 429 trajectories that passed through S 1 /S 0 hopping points, 228 underwent decarbonylation (Φ comp = 53%). The remaining 201 trajectories (47%) reverted to 1. For 2, 464 trajectories crossed to the ground state after 1 ps. 130 of the 464 trajectories corresponded to the decarbonylation reaction (Φ comp = 28%), while 334 trajectories (72%) reverted to cyclopropenone. We plotted the two σ CC bond lengths in 1 and 2 to determine whether the reaction was concerted or stepwise. Figure shows these bond lengths throughout the 1 ps trajectories; the black dots correspond to the S 1 /S 0 hopping points. Figure shows the σ CC distances throughout each of the trajectories. All trajectories with 𝜎 CC bonds exceeding 3.3 Å were considered to be dissociated. The QY for the dissociation reaction of 1 and 2 are 53% and 28%, respectively. Optimized MECI structures for 1 and 2 are shown with yellow points on both plots, and the black dots represent S 1 /S 0 hopping points. The S 1 /S 0 hopping points for 1 and 2 have a large range of 𝜎 CC bond distances (1.36-2.77 Å). We grouped the hopping points structures based on their synchronicities. The blue region corresponds to hopping points with at least one σ CC >1.80 Å and are called asynchronous. The hopping points in the red region correspond to structures with both σ CC bonds <1.80 Å (the FC-region). We calculated the branching ratios for asynchronous and FC-region hopping points to determine if the hopping points' structures influenced this reaction's quantum yields. Only 78 (18%) of the 429 NAMD trajectories of 1 passed through a FC-region hopping point. Of those 78 FC-region hopping points, 75 reverted to the reactant, and only 3 trajectories led to decarbonylation. The remaining 351 (82%) NAMD trajectories passed through asynchronous hopping points. 225 (64%) trajectories correspond to decarbonylation, while 126 (36%) trajectories are not productive and reform 1. 269 (58%) of the 464 trajectories of 2 passed through a FC-region hopping point, and 195 (42%) passed through asynchronous hopping points. Of those 269 FC-region hopping points, 262 hopping points revert to the reactant, and only 7 trajectories trajectories dissociate to the product. 123 of the trajectories (63%) from the asynchronous region undergo photo-decarbonylation dissociate, and 72 trajectories (37%) reform the reactant. Examples of hopping point structures from both seam regions are presented in Figures and. Both the asynchronous hopping point geometries (1as and 2-as) contain one 𝜎 CC bond in the cyclopropenone ring that is fully broken (2.31 Å and 2.36 Å, respectively). In contrast, the other cyclopropenone 𝜎 CC bond is somewhat lengthened from 1-S0 (1.57 and 1.41 Å, respectively). The predistortion of the cyclopropenone ring towards decarbonylation in the asynchronous hopping points results in a preference for productive trajectories. The 𝜎 C2-C5 and 𝜎 C3-C5 bond lengths in the FC hopping points geometries are 1.39 Å and 1.65 Å (1-fc), and 1.36 Å and 1.56 Å (2-fc).