Gómez Cano, Tatiana

Context: The reaction force constant (κ), introduced by Professor Alejandro Toro-Labbé, plays a pivotal role in characterizing the reaction pathway by assessing the curvature of the potential energy profile along the intrinsic reaction coordinate. This study establishes a novel link between κ and the reactivity descriptors of conceptual density functional theory (c-DFT). Specifically, we derive expressions that relate the reaction force constant to nuclear softness and variations in chemical potential. Our findings indicate that regions of the reaction pathway where κ is negative match with significant electronic structure rearrangements, while positive κ regions match mostly with geometric rearrangements. This correlation between κ and c-DFT reactivity descriptors enhances our understanding of the underlying forces driving chemical reactions and offers new perspectives for analyzing reaction mechanisms. Methods: The internal reaction path for the proton transfer in SNOH, chemical potential, and nuclear softness were computed using DFT with B3LYP exchange-correlation functional and 6-311++G(d,2p) basis set.

In pursuing sustainable energy solutions, developing efficient (photo)catalysts for water splitting utilizing low-cost and abundant materials is essential for advancing green hydrogen production technologies. This computational study investigates the potential of lamellar (2D) thiophosphate mixed phases [Figure presented] as a catalyst for the oxygen evolution reaction (OER) in water splitting processes. Employing density functional theory simulations that account for spin–orbit coupling, we demonstrate that incorporating Ni cations significantly reduces the bandgap by approximately 0.7 eV while optimizing the valence band for effective water photo-oxidation. By analyzing free energy pathways for the adsorption of intermediate species during the OER, we identify the formation of [Figure presented] as the crucial step influencing the overpotential in these materials. Notably, the incorporation of Ni cations reduces the overpotential from 1.41 eV in MnPS3 to 1.12 eV in the [Figure presented] mixed phase. Furthermore, when Ni cations are introduced as adatoms on the surface of MnPS3, the overpotential decreases to an impressive 0.29 eV, which is comparable with state-of-the-art catalysts like IrO2. Overall, this study provides valuable computational insights into the potential of 2D [Figure presented] materials as promising alternative catalysts for the OER.