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Energetic Effects of a Closed System Approach Including Explicit Proton and Electron Acceptors as Demonstrated by a Mononuclear Ruthenium Water Oxidation Catalyst
Author(s) -
de Ruiter Jessica M.,
de Groot Huub J. M.,
Buda Francesco
Publication year - 2018
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201801093
Subject(s) - catalysis , ruthenium , proton , chemistry , photochemistry , electron transfer , proton coupled electron transfer , solvent , energetics , molecular dynamics , chemical physics , electron , redox , computational chemistry , inorganic chemistry , organic chemistry , thermodynamics , physics , nuclear physics
Abstract When considering water oxidation catalysis theoretically, accounting for the transfer of protons and electrons from one catalytic intermediate to the next remains challenging: correction factors are usually employed to approximate the energetics of electron and proton transfer. Here these energetics were investigated using a closed system approach, which places the catalytic intermediate in a simulation box including proton and electron acceptors, as well as explicit solvent. As a proof of principle, the first two catalytic steps of the mononuclear ruthenium‐based water oxidation catalyst [Ru(cy)(bpy)(H 2 O)] 2+ were examined using Car‐Parrinello Molecular Dynamics. This investigation shows that this approach offers added insight, not only into the free energy profile between two stable intermediates, but also into how the solvent environment impacts this dynamic evolution.