A complex defect studied through DFT: The Fe3–O2− pair in KMgF3

Electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopies performed by different authors in KMgF3, KZnF3, and RbCdF3 have detected a strongly axial Fe 3 center that was tentatively assigned to a FeF5O 4 complex. The current work is devoted to exploring the properties of the FeF5O 4 center (C4V symmetry) in KMgF3 by means of density functional calculations. The equilibrium distance between Fe 3 and O 2 (1.83 A) is found to be only 10% higher than that computed for the Fe 3 -O 2 pair in vacuo (1.63 A), but 25 pm smaller than that corresponding to FeO6 units. These data together with the charge transferred onto the oxygen in the antibonding a* 1 (3z 2 r 2 ) orbital reveals the formation of a

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