Abstract
Understanding the atomic-level behavior of photocatalysts under hydrated conditions is essential for improving hydrogen production efficiency. In this work, density functional theory calculations and classical all-atom molecular dynamics simulations were performed to investigate the intra- and intermolecular interactions of rod- and cluster-shaped cadmium sulfide in the presence of implicit and explicit water, respectively. The density functional theory optimized geometries, reduced density gradient, noncovalent interaction, critical point, and molecular electrostatic potential maps were examined using the LC-ωPBE functional with the LANL2DZ basis set and the IEFPCM implicit solvation model, while explicit hydration was modeled via classical all-atom molecular dynamics simulations by obtaining molecular snapshots and radial distribution functions. Density functional theory results revealed that rod-shaped cadmium sulfide exhibits stronger directional bonding and higher electronic localization compared to cluster-shaped cadmium sulfide, while classical all-atom molecular dynamics simulations showed that water molecules preferentially interact with surface S atoms of cadmium sulfide sites. This atomistic insight clarifies how morphology and hydration jointly modulate cadmium sulfide electronic structure and reactivity, providing guidance for the rational design of efficient cadmium sulfide-based photocatalysts for solar-driven water splitting.