Nonadiabatic Dynamics in a Continuous Circularly Polarized Laser Field with Floquet Phase-Space Surface Hopping

Abstract

Nonadiabatic chemical reactions involving continuous circularly polarized light (cw CPL) have not attracted as much attention as dynamics in unpolarized/linearly polarized light. However, including circularly (in contrast to linearly) polarized light allows one to effectively introduce a complex-valued time-dependent Hamiltonian, which offers a new path for control or exploration through the introduction of Berry forces. Here, we investigate several inexpensive semiclassical approaches for modeling such nonadiabatic dynamics in the presence of a time-dependent complex-valued Hamiltonian, beginning with a straightforward instantaneous adiabatic fewest-switches surface hopping (IA-FSSH) approach (where the electronic states depend on position and time), continuing to a standard Floquet fewest switches surface hopping (F-FSSH) approach (where the electronic states depend on position and frequency), and ending with an exotic Floquet phase-space surface hopping (F-PSSH) approach (where the electronic states depend on position, frequency, and momentum). Using a set of model systems with time-dependent complex-valued Hamiltonians, we show that the Floquet phase-space adiabats are the optimal choice of basis as far as accounting for Berry phase effects and delivering accuracy. Thus, the F-PSSH algorithm sets the stage for future modeling of nonadiabatic dynamics under strong externally pumped circular polarization.