Dissociation Time, Quantum Yield, and Dynamic Reaction Pathways in the Thermolysis of trans-3,4-Dimethyl-1,2-dioxetane

The thermolysis of trans-3,4-dimethyl-1,2-dioxetane is studied by trajectory surface hopping. The significant difference between long and short dissociation times is rationalized by frustrated dissociations and the time spent in triplet states. If the C-C bond breaks through an excited state channel, then the trajectory passes over a ridge of the potential energy surface of that state. The calculated triplet quantum yields match the experimental results. The dissociation half-times and quantum yields follow the same ascending order as per the product states, justifying the conjecture that the longer dissociation time leads to a higher quantum yield, proposed in the context of the methylation effect. The populations of the molecular Coulomb Hamiltonian and diagonal states reach equilibrium, but the triplet populations with different S_z components fluctuate indefinitely. Certain initial velocities, leading the trajectories to given product states, can be identified as the most characteristic features for sorting trajectories according to their product states.