Surface hopping dynamics using a locally diabatic formalism: Charge transfer in the ethylene dimer cation and excited state dynamics in the 2-pyridone dimer

In this work, the advantages of a locally diabatic propagation of the electronic wave function in surface hopping dynamics proceeding on adiabatic surfaces are presented providing very stable results even in challenging cases of highly peaked nonadiabatic interactions. The method was applied to the simulation of transport phenomena in the stacked ethylene dimer radical cation and the hydrogen bonded 2-pyridone dimer. Systematic tests showed the reliability of the method, in situations where standard methods relying on an adiabatic propagation of the wave function and explicit calculation of the nonadiabatic coupling terms exhibited significant numerical instabilities. Investigations of the ethylene dimer radical cation with an intermolecular distance of 7.0 Å provided a quantitative description of diabatic charge trapping. For the 2-pyidone dimer, a complex dynamics was obtained: a very fast (<10 fs) initial S₂/S₁ internal conversion; subsequent excitation energy transfers with a characteristic time of 207 fs; and the occurrence of proton coupled electron transfer (PCET) in 26% of the trajectories. The computed characteristic excitation energy transfer time of 207 fs is in satisfactory agreement with the experimental value of 318 fs derived from the vibronic exciton splittings in a monodeuterated 2-pyridone dimer complex. The importance of nonadiabatic coupling for the PCET related to the electron transfer was demonstrated by the dynamics simulations