Communication: Predictive partial linearized path integral simulation of condensed phase electron transfer dynamics.

Area of Science:

• Quantum chemistry
• Chemical kinetics
• Electron transfer theory

Background:

• Electron transfer (ET) is fundamental in chemistry and biology.
• Accurate ET rate calculations are crucial for understanding reaction dynamics.
• Existing semi-classical methods face limitations across different electronic coupling regimes.

Purpose of the Study:

• To develop and validate a novel partial linearized path integral approach for calculating condensed phase ET rates.
• To assess the accuracy of this method compared to traditional semi-classical techniques.
• To demonstrate its capability in capturing key ET phenomena like the Marcus turnover and electronic coherence.

Main Methods:

• Utilizing a partial linearized path integral formulation.
• Directly evaluating quantum time correlation functions (flux-flux/flux-side).
• Applying the method to a model system with varied electronic couplings and thermodynamic driving forces.

Main Results:

• The approach accurately transitions between non-adiabatic and adiabatic regimes, outperforming semi-classical methods.
• It reliably reproduces the Marcus turnover across four orders of magnitude in driving force.
• Accurate rate predictions were achieved over five orders of magnitude in inverse temperature.
• Electronic coherence effects influencing the inverted regime were correctly captured.

Conclusions:

• The partial linearized path integral method offers a robust and accurate tool for condensed phase ET rate calculations.
• This approach provides superior accuracy across a wide range of electronic couplings and thermodynamic conditions.
• It successfully models complex phenomena like the Marcus inverted region, offering insights into electronic coherence.