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Momentum-dependent band spin splitting in semiconducting MnO2: a density functional calculation

Recently, manganese-oxide compounds have attracted considerable attention, in particular, as candidate materials for photochemical water-splitting reactions. Here, we investigate electronic states of pristine manganese dioxides (MnO2) in different crystal phases using spin-polarized density function...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2016-05, Vol.18 (19), p.13294-13303
Main Authors: Noda, Yusuke, Ohno, Kaoru, Nakamura, Shinichiro
Format: Article
Language:English
Online Access:Get full text
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Summary:Recently, manganese-oxide compounds have attracted considerable attention, in particular, as candidate materials for photochemical water-splitting reactions. Here, we investigate electronic states of pristine manganese dioxides (MnO2) in different crystal phases using spin-polarized density functional theory (DFT) with Hubbard U correction. Geometrical structures and band dispersions of α-, β-, δ-, and λ-MnO2 crystals with collinear magnetic [ferromagnetic (FM) and antiferromagnetic (AFM)] orders are discussed in detail. We reveal that penalty energies that arise by violating the Goodenough-Kanamori rule are important and the origin of the magnetic interactions of the MnO2 crystals is governed by the superexchange interactions of Mn-O-Mn groups. In addition, it is found that momentum-dependent band spin splitting occurs in the AFM α-, β-, and δ-MnO2 crystals while no spin splitting occurs in the AFM λ-MnO2 crystal. Our results show that spin-split band dispersions stem from the different orientations of Mn-centred oxygen octahedra. Such interesting electronic states of the MnO2 crystals are unraveled by our discussion on the relationship between the effective (spin-dependent) single-electron potentials and the space-group symmetry operations that map up-spin Mn atoms onto down-spin Mn atoms. This work provides a basis to understand the relationship between the spin-dependent electronic states and the crystallography of manganese oxides. Another relationship to the recent experimental observations of the photochemical oxygen evolution of MnO2 crystals is also discussed.
ISSN:1463-9084
DOI:10.1039/c5cp07806g