| Summary: | Addressing the urgent need for sustainable energy sources, this study investigates the intricate relationship between rhodium (Rh<sub>5</sub>) nanoclusters and TiO<sub>2</sub> rutile (110) surfaces, aiming to advance photocatalytic water splitting for green hydrogen production. Motivated by the imperative to transition from conventional fossil fuels, this study employs density functional theory (DFT) with DFT-D3 and HSE06 hybrid functionals to analyse the geometrical stabilities and electronic structures of Rh<sub>5</sub> nanoclusters on TiO<sub>2</sub> rutile (110). TiO<sub>2</sub>, a prominent photocatalyst, faces challenges such as limited visible light absorption, leading researchers to explore noble metals like Rh as cocatalysts. Our results show that bipyramidal Rh<sub>5</sub> nanoclusters exhibit enhanced stability and charge transfer when adsorbed on TiO<sub>2</sub> rutile (110) compared to trapezoidal configurations. The most stable adsorption induces the oxidation of the nanocluster, altering the electronic structure of TiO<sub>2</sub>. Extending the analysis to defective TiO<sub>2</sub> surfaces, this study explores the impact of Rh<sub>5</sub> nanoclusters on oxygen vacancy formation, revealing the stabilisation of TiO<sub>2</sub> and increased oxygen vacancy formation energy. This theoretical exploration contributes insights into the potential of Rh<sub>5</sub> nanoclusters as efficient cocatalysts for TiO<sub>2</sub>-based photocatalytic systems, laying the foundation for experimental validations and the rational design of highly efficient photocatalysts for sustainable hydrogen production. The observed effects on electronic structures and oxygen vacancy formation emphasize the complex interactions between Rh<sub>5</sub> nanoclusters and the TiO<sub>2</sub> surface, guiding future research in the quest for clean energy alternatives.
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