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.