Magnetic interactions in the catalyst used by nature to split water: a DFT + U multiscale study on the Mn4CaO5 core in photosystem II

An important approach in the design of new environmentally friendly materials is represented by the study of analogous systems already existing in nature. In the search for new water splitting catalysts, the corresponding natural analogue is represented by the oxygen-evolving complex of photosystem II, which is a large membrane protein complex present in photosynthetic organisms. The understanding of the catalytic strategy of its active Mn4CaO5 core is important to unravel the mechanisms of water oxidation in photosynthesis and can serve as an inspiring model for the design of biomimetic catalysts based on largely non-toxic, earth abundant elements. The magnetic interactions between Mn ions are studied in the present work by means of DFT+U broken symmetry ab initio molecular dynamics within a quantummechanics/molecular mechanics framework. The room temperature dynamics of two different structural models (i.e. with total high-spin and total low-spin ground states) was stable during the simulated time. We observed large fluctuations of the magnetic coupling 3 Author to whom any correspondence should be addressed. Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distribution of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI. New Journal of Physics 16 (2014) 01502