Surface hopping molecular dynamics simulation of ultrafast methyl iodide photodissociation mapped by Coulomb...

We present a highly efficient approach to directly and reliably simulate photodissociation followed by Coulomb explosion of methyl iodide. In order to achieve statistical reliability, more than 40 000 trajectories are calculated on accurate potential energy surfaces of both the neutral molecule and the doubly charged cation. Non-adiabatic effects during photodissociation are treated using a Landau-Zener surface hopping algorithm. The simulation is performed analogous to a recent pump-probe experiment using coincident ion momentum imaging [Ziaee et al., Phys. Chem. Chem. Phys., 2023, 25, 9999-10010]. At large pump-probe delays, the simulated delay-dependent kinetic energy release signals show overall good agreement with the experiment, with two major dissociation channels leading to I(²P_3/2) and I*(²P_1/2) products. At short pump-probe delays, the simulated kinetic energy release differs significantly from the values obtained by a purely Coulombic approximation or a one-dimensional description of the dicationic potential energy surfaces, and shows a clear bifurcation near 12 fs, owing to non-adiabatic transitions through a conical intersection. The proposed approach is particularly suitable and efficient in simulating processes that highly rely on statistics or for identifying rare reaction channels.