Numerical tests of coherence-corrected surface hopping methods using a donor-bridge-acceptor model system.

Area of Science:

• Quantum chemistry
• Computational chemistry
• Chemical dynamics

Background:

• Surface hopping (SH) is a mixed quantum-classical method for excited state processes.
• Classical nuclear trajectories in SH can cause overcoherence, leading to inaccurate reaction rates.
• Existing decoherence corrections for SH lack comprehensive benchmarking.

Purpose of the Study:

• To benchmark common decoherence-corrected surface hopping methods.
• To evaluate the accuracy of Truhlar's decay-of-mixing (DOM) and Subotnik's augmented SH.
• To provide insights into selecting appropriate decoherence methods for nonadiabatic dynamics.

Main Methods:

• Numerical simulations of donor-bridge-acceptor (DbA) model systems.
• Comparison of augmented SH and DOM methods against Marcus theory.
• Development of a parameterization strategy for DOM decoherence rates.

Main Results:

• Augmented SH quantitatively recovers Marcus theory predictions for reaction rates.
• DOM shows only qualitative accuracy, highly dependent on parameterization.
• The proposed DOM parameterization improves reaction rate accuracy and transferability.

Conclusions:

• Careful selection of decoherence methods is crucial for accurate SH simulations.
• Augmented SH offers a reliable approach for modeling nonadiabatic charge transfer.
• This study provides valuable benchmarks for advancing mixed quantum-classical methods.