A B3LYP study on electronic structures of [(X)<sub>m</sub>Mn(<i>μ</i>-oxo)<sub>2</sub>Mn(Y)<sub>n</sub>]<sup><i>q</i>+</sup> (X, Y = H<sub>2</sub>O, OH and O) as a Mn cluster model of OEC — Oak Academic Publishing
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A B3LYP study on electronic structures of [(X)<sub>m</sub>Mn(<i>μ</i>-oxo)<sub>2</sub>Mn(Y)<sub>n</sub>]<sup><i>q</i>+</sup> (X, Y = H<sub>2</sub>O, OH and O) as a Mn cluster model of OEC
Chemistry Department for Materials, Graduate School of Engineering, Mie University, Tsu, Japan
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Chemistry Department for Materials, Graduate School of Engineering, Mie University, Tsu, Japan
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Chemistry Department for Materials, Graduate School of Engineering, Mie University, Tsu, Japan
1 Chemistry Department for Materials, Graduate School of Engineering, Mie University, Tsu, Japan
2 Chemistry Department for Materials, Graduate School of Engineering, Mie University, Tsu, Japan
3 Chemistry Department for Materials, Graduate School of Engineering, Mie University, Tsu, Japan
Electronic and molecular structures of [(X) m Mn( μ -oxo) 2 Mn(Y) n ] q + (X, Y = H 2 O, OH and O), which are Mn cluster models at catalytic sites of OEC, were studied by broken-symmetry unrestricted B3LYP method. Two paths from the S 0 to S 3 states of Kok cycle were investigated. One is a path starting from [Mn(II) ( μ -oxo) 2 Mn(III)] at the S 0 state, and another is from [Mn(III) ( μ -oxo) 2 Mn(III)] at the S 0 . Results found in this study are summarized as, 1) In [Mn(II), Mn(III)], it is not possible that H 2 O molecules coordinate to the Mn atoms with retaining the octahedral configuration. 2) The OHˉ anion selectively coordinates to Mn(IV) rather than Mn(III). 3) When the oxo atom directly bind to the Mn atom, the Mn atom must be a Mn(IV). From these results, the catalytic mechanism for four-electron oxidation of two H 2 O molecules in OEC is proposed. 1) The Mn 4 (II, III, IV, IV) at S 0 is ruled out. 2) For Mn 4 (III, III, IV, IV) at S 1 , the Mn atom coordinated by OHˉ anion is a Mn(IV) not Mn(III). 3) Only Mn(III) ion which is coordinated by a H 2 O molecule at S 0 plays crucial roles for the oxidation.
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