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Evaluation of new low-valent computational models for the oxygen-evolving complex of photosystem II

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Pantazis,  Dimitrios A.
Research Group Pantazis, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Pantazis, D. A. (2020). Evaluation of new low-valent computational models for the oxygen-evolving complex of photosystem II. Chemical Physics Letters, 753(8): 137629. doi:10.1016/j.cplett.2020.137629.


Cite as: http://hdl.handle.net/21.11116/0000-0006-B455-F
Abstract
The oxidation states of the Mn4CaO5 cluster of the photosynthetic oxygen-evolving complex remain controversial. New quantum chemical models for the dark-stable S1 state suggest that a low-valent Mn(III-IV-III-II) form, opposed to the commonly accepted high-valent Mn(III-IV-IV-III) assignment, agrees with available structural data. We examine the magnetic properties of the models and the consequences for electronic structure and catalytic progression of assuming a neutral second-sphere residue D1-His337. The low-valent model reproduces the experimental diamagnetic ground spin-state. However, the protonation assignment introduces a critical flaw because neutral His337 becomes itself the locus of subsequent oxidation, in contradiction to physiological catalytic progression.