Fukui Function and Fukui Potential for Solid-State Chemistry: Application to Surface Reactivity.

Area of Science:

• Computational Chemistry
• Materials Science
• Surface Chemistry

Background:

• Conceptual density functional theory (c-DFT) is vital for understanding chemical reactivity.
• Applying c-DFT to extended systems with periodic boundary conditions (PBC) presents formal and technical challenges.
• The Fukui function and its potential are key reactivity descriptors, but their calculation in extended systems is complex.

Purpose of the Study:

• To investigate the calculation of the Fukui function and potential in systems with periodic boundary conditions (PBC).
• To evaluate the impact of a fictitious potential from a compensating background of charge (CBC) on reactivity descriptors.
• To explore computational approaches for accurate surface reactivity prediction in diverse materials.

Main Methods:

• Analysis of metallic and semiconductor surfaces (Ti, Pt, TiO2, SnO2, MgO, TiC, ZrC).
• Investigation of fictitious potentials associated with compensating background of charge (CBC).
• Comparison of various computational methods, including finite differences with self-consistent potential correction and interpolation methods.

Main Results:

• Certain computational methods yield reliable Fukui function and potential values for extended systems, while others introduce artifacts.
• Finite differences with self-consistent potential correction is advocated for accurate calculations.
• A reliable Fukui potential calculation method, combined with perturbation theory, can predict interaction energies for surface reactions.

Conclusions:

• This work provides practical methodologies to overcome challenges in predicting surface reactivity using c-DFT.
• The findings enhance theoretical frameworks for Fukui function calculations under PBC.
• The study equips researchers with robust tools for advancing materials science and surface chemistry, particularly in heterogeneous catalysis.