Transition from Mn4+ to Mn3+ induced by surface reconstruction at λ-MnO2(001)

Structural and electronic properties of the lambda-MnO2(001) surface are investigated applying density functional theory approach. The calculations show that all Mn ions at unreconstructed smooth surface preserve the +4 oxidation state observed in the bulk. Upon the lambda-MnO2(001) reconstruction, one fourth of Mn ions at the surface undergo a change of the oxidation state from +4 to +3, although the reconstruction does not change the Mn coordination number with oxygen. This is accompanied with the filling of initially empty 3d(z2) states localized on cations with one electron denoted by two neighboring O atoms. Although the reconstruction leads to an energy gain of 0.04 eV per surface unit cell, it is not a spontaneous process since it proceeds with an activation energy of 0.12 eV. (C) 2010 American Institute of Physics. [doi:10.1063/1.3509401]