A practical computational protocol for photocatalytic reactions beyond ground-state approximations.

Area of Science:

• Computational Chemistry
• Materials Science
• Photocatalysis

Background:

• Current theoretical studies on heterogeneous photocatalysts rely on ground-state Density Functional Theory (DFT).
• Ground-state DFT calculations do not accurately represent the excited-state physics essential for light-driven chemical processes.
• Accurate theoretical modeling is vital for designing efficient photocatalysts.

Purpose of the Study:

• To develop and present a novel computational protocol that incorporates excited states into Gibbs free energy diagrams.
• To address the limitations of ground-state DFT in modeling photocatalytic mechanisms.
• To provide a more accurate theoretical framework for understanding light-driven reactions in heterogeneous systems.

Main Methods:

• Development of a new computational protocol considering excited states.
• Application of the protocol to Gibbs free energy diagrams.
• Utilizing Density Functional Theory (DFT) with excited-state considerations.

Main Results:

• The new protocol explicitly includes excited states in the analysis of photocatalytic reactions.
• The method was successfully applied to prototypical water oxidation and oxygen reduction reactions.
• The study focused on a single-atom Cobalt (Co) embedded graphitic carbon nitride (g-C3N4) cocatalyst.

Conclusions:

• The presented computational protocol offers a more physically realistic approach to studying photocatalysts.
• Explicitly considering excited states enhances the understanding of light-driven processes.
• This work provides a foundation for more accurate theoretical predictions of photocatalyst performance.