Theoretical investigation of molecular and electronic structure changes of the molecular magnet Mn12 cluster upon super-reduction.

Density functional theory calculations on the neutral [Mn12]0 molecular magnet and super‐reduced [Mn12]8– cluster were employed to investigate the experimental geometrical changes observed during discharging in a molecular cluster battery. It was found that for relevant low‐spin states the eight electrons added in [Mn12]8– are mainly added to the outer eight Mn atoms, causing elongation of the bonds between outer Mn and their surrounding O atoms, while the inner Mn4 cluster is less affected by the reduction. Schematic representation of the spin density of the neutral [Mn12]0 cluster and its super‐reduced state [Mn12]8–, for which several possible spin states were found. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) Part of Focus Issue on “Functional Oxides” (Eds.: T. Frauenheim, J. M. Knaup, P. Broqvist, S. Ramanathan) DFT‐based theoretical studies describe the changes in molecular and electronic structures during the super‐reduction of the Mn12 cluster by the uptake of 8 excess electrons in the gas phase. The results agree largely with experimental observations obtained in a molecular cluster battery setup. [ABSTRACT FROM AUTHOR]