First Principles Description of the Valence States in Manganese Oxides

Abstract

First principles periodic Hartree-Fock calculations of Li:MnO, Li_xMnO₂ and CaMnO₃ are reported from which direct evidence is presented to indicate that the valence state of Mn remains essentially d⁵ throughout the series. The net spin moment on Mn, on the other hand, follows that convential change from ∼5μ_B to ∼3μ_B associated with the valence states Mn(II), Mn(III), Mn(IV).