Validating fewest-switches surface hopping in the presence of laser fields

The capability of fewest-switches surface hopping (FSSH) to describe non-adiabatic dynamics under explicit excitation with external fields is evaluated. Different FSSH parameters are benchmarked against multi-configurational time dependent Hartree (MCTDH) reference calculations using SO2 and 2-thiocytosine as model, yet realistic, molecular systems. Qualitatively, FSSH is able to reproduce the trends in the MCTDH dynamics with (also without) an explicit external field; however, no set of FSSH parameters is ideal. The adequate treatment of the overcoherence in FSSH is revealed as the driving factor to improve the description of the excitation process with respect to the MCTDH reference. Here, two corrections were tested: the augmented-FSSH (AFSSH) correction and the energy-based decoherence correction. A dependence on the employed basis is detected in AFSSH, performing better when spin-orbit and external laser field couplings are treated as off-diagonal elements instead of projecting them onto the diagonal of the Hamilton operator. In the presence of an electric field, the excited state dynamics was found to depend strongly on the vector used to rescale the kinetic energy along after a transition between surfaces. For SO2, recurrence of the excited wave packet throughout the duration of the applied laser pulse is observed for laser pulses (>100 fs), resulting in additional interferences missed by FSSH and only visible in variational multi-configurational Gaussian when utilizing a large number of Gaussian basis functions. This feature vanishes when going toward larger molecules, such as 2-thiocytosine, where this effect is barely visible in a laser pulse 200 fs long.

Automated summary

This study evaluates the capability of fewest-switches surface hopping (FSSH) in describing non-adiabatic dynamics under external fields, finding that FSSH is able to reproduce trends in multi-configurational time dependent Hartree (MCTDH) reference calculations but no ideal set of parameters exists. Adequate treatment of overcoherence in FSSH is crucial for improving the description of excitation processes.