Abstract
We present a molecular mechanics force field in AMBER format for the mixed-valence manganese vanadium oxide cluster [Mn4V4O17(OAc)3]3−—a synthetic analogue of the oxygen-evolving complex that catalyzes the water oxidation reaction in photosystem II—with parameter sets for two different oxidation states. Most force field parameters involving metal atoms have been newly parametrized and the harmonic terms refined using hybrid quantum mechanics/molecular mechanics reference simulations, although some parameters were adapted from pre-existing force fields of vanadate cages and manganese oxo dimers. The characteristic Jahn–Teller distortions of d4 MnIII ions in octahedral environments are recovered by the force field. As an application, the developed parameters have been used to calculate the redox potential of the [MnIIIMn3IV] ⇌ [Mn4IV]+e− half-reaction in acetonitrile by means of Marcus theory.
Highlights
There is a large consensus among scientists that global warming threatens life on Earth as we know it [1]
The assignment of atom types is shown in panels (c–e), where each panel shows a different subset of the entire connectivity network to avoid occlusion
We have developed a force field in AMBER format for a manganese vanadium oxide synthetic analogue of the oxygen evolving complex, which catalyzes the water splitting reaction in nature
Summary
There is a large consensus among scientists that global warming threatens life on Earth as we know it [1]. Artificial photosynthesis—photochemically driven water splitting [3]—is emerging as a promising and clean technology to convert sunlight into a storable energy form Devices for this task consist of several components, where the water oxidation catalyst is among the most critical ones [4,5,6,7,8,9]. The outstanding efficiency of the natural OEC makes it an appealing model for the development of analogous artificial water oxidation catalysts (WOCs). Based on this idea, several synthetic WOCs based on metal oxide clusters—polyoxometalates (POMs)—have shown promising catalytic activities towards the water oxidation reaction [5,6,7,8,10].
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