Electron transfer in confined electromagnetic fields

Area of Science:

• Quantum physics
• Molecular electronics
• Nanophotonics

Background:

• Cavity quantum electrodynamics (cQED) explores light-matter interactions.
• Nanophotonics enables control over light at the nanoscale.
• Electron transfer is crucial in molecular systems.

Purpose of the Study:

• To investigate nonadiabatic electron transfer in a confined cavity field.
• To develop a generalized framework for molecular-cavity interactions.
• To explore rate enhancement in electron transfer processes.

Main Methods:

• Developed a generalized Hamiltonian for charged molecular systems and quantized cavity fields.
• Applied the framework to donor-acceptor electron transfer within a cavity.
• Analyzed two limiting cases: fast and slow electron tunneling relative to the cavity mode.

Main Results:

• The effective system Hamiltonian unifies Rabi and spin-boson models with a self-dipole term.
• Significant electron transfer rate enhancement observed in the Marcus inverted region.
• Coupling to the cavity mode is shown to be a key factor in rate enhancement.

Conclusions:

• Coupling molecular systems to cavity modes offers a pathway to control electron transfer.
• Visible and infrared plasmonics can be utilized to manipulate electron transfer processes.
• This work opens new avenues for designing molecular electronic devices.