An Accurate Linearized Semiclassical Approach for Calculating Cavity-Modified Charge Transfer Rate Constants

Area of Science:

• Computational Chemistry
• Quantum Dynamics
• Chemical Physics

Background:

• Cavity quantum electrodynamics offers novel ways to control chemical reactions.
• Understanding charge transfer reactions in microcavities is crucial for designing new chemical processes.

Purpose of the Study:

• To develop a scalable and accurate computational framework for charge transfer reactions in microcavities.
• To investigate the role of linearization approximations in capturing cavity effects.

Main Methods:

• Combining linearized semiclassical approximation with Fermi's golden rule (FGR) rate theory.
• Employing partial and full linearization with respect to nuclear, photonic, and electronic degrees of freedom.
• Utilizing the Wigner transforms of the product (WoP) of operators.

Main Results:

• The developed framework accurately captures cavity-induced rate enhancement in charge transfer reactions.
• Both partial and full linearization methods show high accuracy.
• The partial linearization method yields quantum-mechanically exact results for a specific model system when WoP is applied.

Conclusions:

• The new computational framework is general-purpose, cost-effective, and scalable.
• Accurate prediction of cavity effects on reaction rates is achievable.
• The importance of the Wigner transforms of the product (WoP) is highlighted for accurate results.