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Ab Initio Molecular Dynamics Study of Water Oxidation Reaction Pathways in Mono‐Ru Catalysts
Author(s) -
VallésPardo José Luis,
Guijt Marieke C.,
Iannuzzi Marcella,
Joya Khurram S.,
de Groot Huub J. M.,
Buda Francesco
Publication year - 2012
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201100546
Subject(s) - chemistry , catalysis , hydronium , catalytic cycle , ab initio , molecular dynamics , computational chemistry , redox , reaction intermediate , photochemistry , ab initio quantum chemistry methods , bond cleavage , reaction coordinate , ion , inorganic chemistry , molecule , organic chemistry
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 OO 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 OO bond formation is quickly followed by a proton transfer leading to a RuOOH 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.