Eu-Mn Charge Transfer and the Strong Charge-Spin-Electronic Coupling Behavior in EuMnO3.

ABSTRACT

Based on first-principles calculations with the DFT + U method, the couplings of lattice, charge, spin, and electronic behaviors underlying the Eu-Mn charge transfer in a strongly correlated system of EuMnO3 were investigated. The potential valence transition from Eu3+/Mn3+ to Eu2+/Mn4+ was observed in a compressed lattice with little distortions, which is achieved under hydrostatic pressure and external strain. The intraplane antiferromagnetism (AFM) of Mn is proved to be instrumental in the emergence of Eu2+. Furthermore, we calculated the magnetic exchange interactions within two equilibrium structures of Eu3+Mn3+O3 and Eu2+Mn4+O3. Mn-Mn ferromagnetic exchange in the ab-plane is enhanced strongly in the Eu2+Mn4+O3 structure, contributing to the existence of mixed states. The versatile electronic structures were obtained within the Eu2+Mn4+O3 phase by imposing different magnetic configurations on the Eu and Mn sublattice, attributed to the coupling of charge transfer and magnetic orderings. It is found that the intraplane ferromagnetic ordering of Mn leads to a metallic electronic structure with the coexistence of Eu2+ and Eu3+, while the intraplane AFM Mn spin ordering leads to insulating states only with Eu2+. Notably, a half-metallic characteristic emerges at the magnetic ground state of CF ordering (C-type AFM for the Eu sublattice and ferromagnetic for the Mn sublattice), which makes such a supposed phase more intriguing than the conventional experimental phase. Additionally, the mixture of delocalized 4f with 5d states of Eu in the background of Mn 3d and O 2p orbitals implies a pathway of Eu 4f 5d ↔ O 2p ↔ Mn 3d for charge transfer between Eu and Mn. Our calculation shows that the Eu-Mn charge transfer could be expected in compressed EuMnO3 and the introduction of Eu2+ 4f states near the Fermi level plays an important role in manipulating the interlinks of charge and spin together with electronic behaviors.