Stimulated and co-operative electron transfer in energy conversion and catalysis

Area of Science:

• Physical Chemistry
• Biochemistry
• Materials Science

Background:

• Electron transfer is fundamental to many biological and chemical processes.
• Current understanding often involves limitations in rate and efficiency for complex systems.
• Cooperative phenomena in electron transfer are crucial for catalysis.

Purpose of the Study:

• To introduce and analyze a new mechanism: stimulated electron transfer.
• To investigate how electronic feedback influences electron transfer rates and energy propagation.
• To explore the potential of this mechanism in biological and artificial systems.

Main Methods:

• Development of a semiclassical kinetic model for chain redox reactions.
• Incorporation of autocatalytic feedback on individual rate constants.
• Minimization of reaction steps to model a continuous electron transfer pathway with feedback.

Main Results:

• Demonstrated drastic increases in electron transfer rate and free energy propagation via electronic feedback.
• Analyzed the impact of pathway inhomogeneities, asymmetries, and vectorial components.
• Showcased acceleration of individual and multiple electron transfers as a function of feedback intensity.

Conclusions:

• Stimulated electron transfer, driven by autocatalytic feedback, offers a new paradigm for efficient electron transfer.
• This mechanism provides a potential explanation for efficient biological electron transfer and multi-electron catalysis.
• It presents a significant challenge and opportunity for artificial photosynthesis and fuel cycle development.