Mapping Proton-Coupled Electron Transfer With Real Space Coordinates

Area of Science:

• Chemical Physics
• Theoretical Chemistry
• Biophysical Chemistry

Background:

• Electron transfer (ET) and proton transfer (PT) are fundamental in energy conversion.
• Proton-coupled electron transfer (PCET) combines ET and PT, requiring specialized theoretical frameworks.
• Existing models lack structural insights into nuclear motion contributions to PCET.

Purpose of the Study:

• To develop a computational approach for mapping PCET square schemes onto real-space coordinates.
• To generate ground and excited-state potential energy surfaces from these mappings.
• To provide structural insights into PCET mechanisms and differentiate between various scenarios.

Main Methods:

• Mapping theoretical PCET square schemes onto real-space coordinates (Å).
• Identifying specific proton transfer (PT) and electron transfer (ET) coordinates.
• Reconstructing potential energy surfaces in orthogonalized coordinates.

Main Results:

• The computational approach generates potential energy surfaces for PCET processes.
• Qualitative differences in surface features were observed for concerted proton-electron transfer and hydrogen atom transfer.
• These differences offer a means to distinguish between distinct PCET mechanisms.

Conclusions:

• The developed method provides a valuable tool for understanding PCET reactions.
• It bridges the gap between theoretical models and real-space structural insights.
• This approach can aid in distinguishing between different types of PCET, crucial for energy conversion studies.