Ab Initio Molecular Dynamics Study of Water Oxidation Reaction Pathways in Mono-Ru Catalysts

✍ Scribed by José Luis Vallés-Pardo; Marieke C. Guijt; Dr. Marcella Iannuzzi; Dr. Khurram S. Joya; Prof. Dr. Huub J. M. de Groot; Dr. Francesco Buda

• Book ID: 102810183
• Publisher: John Wiley and Sons
• Year: 2011
• Tongue: English
• Weight: 657 KB
• Volume: 13
• Category: Article
• ISSN: 1439-4235
• DOI: 10.1002/cphc.201100546

✦ Synopsis

Abstract

Ab initio molecular dynamics simulations with an adaptive biasing potential are carried out to study the reaction path in mononuclear Ru catalysts for water oxidation of the type [(Ar)Ru(X)(bpy)]^+^ with different aromatic ligands (Ar). The critical step of the OO bond formation in the catalytic cycle starting from the [(Ar)Ru(O)(bpy)]^2+^ intermediate is analyzed in detail. It is shown that an explicit inclusion of the solvent environment is essential for a realistic description of the reaction path. Clear evidence is presented for a concerted reaction in which the OO bond formation is quickly followed by a proton transfer leading to a RuOOH intermediate and a hydronium ion. An alternative path in which the approaching water first coordinates to the metal centre is also investigated, and it is found to induce a structural instability of the catalyst with the breaking of the aromatic ligand coordination bond.