Nonadiabatic Dynamics with Exact Factorization: Implementation and Assessment.

Abstract

In this work, we report our implementation of several independent-trajectory mixed-quantum-classical (ITMQC) nonadiabatic dynamics methods based on exact factorization (XF) in the Libra package for nonadiabatic and excited-state dynamics. Namely, the exact factorization surface hopping (SHXF), mixed quantum-classical dynamics (MQCXF), and mean-field (MFXF) are introduced. Performance of these methods is compared to that of several traditional surface hopping schemes, such as the fewest-switches surface hopping (FSSH), branching-corrected surface hopping (BCSH), and the simplified decay of mixing (SDM), as well as conventional Ehrenfest (mean-field, MF) method. Based on a comprehensive set of 1D model Hamiltonians, we find the ranking SHXF ≈ MQCXF > BCSH > SDM > FSSH ≫ MF, with the BCSH sometimes outperforming the XF methods in terms of describing coherences. Although the MFXF method can yield reasonable populations and coherences for some cases, it does not conserve the total energy and is therefore not recommended. We also find that the branching correction for auxiliary trajectories is important for the XF methods to yield accurate populations and coherences. However, the branching correction can worsen the quality of the energy conservation in the MQCXF. Finally, we find that using the time-dependent Gaussian width approximation used in the XF methods for computing decoherence correction can improve the quality of energy conservation in the MQCXF dynamics. The parameter-free scheme of Subotnik for computing the Gaussian widths is found to deliver the best performance in situations where such widths are not known a priori.