Khan, SohiniSohiniKhanPatrikar, KalyaniKalyaniPatrikarSewak, RamRamSewakMondal, AnirbanAnirbanMondal2025-08-312025-08-312025-06-0410.1021/acsami.5c030692-s2.0-105005863279https://d8.irins.org/handle/IITG2025/2809840405555We present the application of the Marcus-Hush formalism as a theoretical framework to investigate charge transfer dynamics in ligand-protected Au systems. By integrating key parameters such as energy level differences and electronic coupling, this approach enables the prediction of photocatalytic efficiency in electron-driven water splitting. Simulations of diverse ligand-functionalized AuNPs establish a clear correlation between charge transfer rates and hydrogen evolution, specifically for functionalized AuNPs bearing aromatic thiols with various para-substituents. Additionally, we extend this framework to selenol-substituted systems, revealing that while selenols perform comparably to thiols in some cases, they do not consistently enhance photocatalytic activity. Beyond electron-driven hydrogen production, we further explore the role of ligand chemistry in modulating hole transfer processes relevant to oxidative half-reactions. In this context, the OH-thiol ligand-functionalized AuNP emerges as the most effective photocatalyst for hole-driven reactions. Overall, this study provides a systematic methodology for screening and designing ligand-functionalized AuNP photocatalysts, offering mechanistic insights into how ligand properties govern photocatalytic performance.falseand reorganization energy | charge transfer kinetics | electronic coupling | interface engineering | ligand-functionalized gold nanoparticles | Marcus−Hush formalism | photocatalytic water splittingArticle1944825232306-323154 June 20250arJournal0WOS:001494651000001