First Principles Description of the Valence States in Manganese Oxides

First principles periodic Hartree-Fock calculations of Li:MnO, Li x M n O 2 and CaMnO 3 are reported from which direct evidence is presented to indicate that the valence state of Mn remains essentially d 5 throughout the series. The net spin moment on Mn, on the other hand, follows that convential change from ∼ 5μ B to ∼ 3 μ B associated with the valence states Mn(ll), Mn(III), Mn(lV).