Study of the Decoherence Correction Derived from the Exact Factorization Approach for Nonadiabatic Dynamics

Area of Science:

• Quantum chemistry
• Computational chemistry
• Chemical dynamics

Background:

• Surface hopping is a key method for simulating nonadiabatic dynamics.
• Accurate simulations require accounting for decoherence effects.
• The exact factorization approach offers a new route to decoherence correction.

Purpose of the Study:

• To present a detailed study of a new decoherence correction for surface hopping.
• To compare this correction with existing methods.
• To evaluate the performance across different molecular systems.

Main Methods:

• Ab initio multiple spawning calculations were employed.
• Three molecules (ethylene, methaniminium cation, fulvene) were studied after photoexcitation.
• Comparisons were made with Granucci-Persico and augmented fewest-switches methods.

Main Results:

• The new decoherence correction was analyzed in detail.
• All three decoherence-corrected methods showed qualitative differences in individual trajectories.
• Averaged dynamics across trajectories were similar for the studied systems.

Conclusions:

• The studied decoherence corrections exhibit distinct trajectory-level behaviors.
• Despite differences, averaged dynamics show robustness across methods for these systems.
• This work validates the new decoherence correction within the exact factorization framework.