Atomic-Scale Understanding of Doping Effects in BaTiO₃ in the Presence of Water: Implications for Photocatalytic Water Splitting

The search for efficient photocatalysts for sustainable hydrogen production has driven growing interest in barium titanate (BaTiO₃)-based materials, particularly through polymorph control, surface engineering, and nonmetal and transition-metal doping. In this work, we provide an atomic-scale understanding of structural modifications in nitrogen-, fluorine-, and rhodium-doped BaTiO₃ using Density Functional Theory (DFT), as well as pristine and fluorine-substituted BaTiO₃ using reactive force-field molecular dynamics (ReaxFF-MD) simulations. DFT results for pristine and doped tetragonal BaTiO₃, as well as pristine hexagonal BaTiO₃, reveal that nitrogen and rhodium substitutions enhance the covalent character of Ti-N and Rh-O bonds and promote the redistribution of electron density, as evidenced by noncovalent interaction (NCI) and critical point (QTAIM) analyses, whereas fluorine substitution leads to more ionic Ti-F bonding. ReaxFF-MD simulations of pristine and fluorine-substituted BaTiO₃ in contact with water molecules demonstrate that fluorine substitution suppresses interfacial O-H bond formation and promotes ordered molecular hydration layers near titanium sites, as reflected in bond statistics and radial distribution functions. This study provides molecular insights into the role of N, F, and Rh doping in BaTiO₃ using DFT, and the role of fluorine doping in BaTiO₃ at the water–solid interface using ReaxFF-MD simulations, demonstrating that this integrated computational approach provides a solid basis for the rational design of next-generation materials for energy-related applications. Direct calculations of photocatalytic activity, charge transfer rates, and ferroelectric polarization effects were not performed in this work and remain important directions for future study.