The importance of electronic correlations in exploring the exotic phase diagram of layered Li${}_x$MnO${}_2$

Abstract

Using ab initio dynamical mean-field theory we explore the electronic and magnetic states of layered Li${}_x$MnO${}_2$ as a function of $x$, the state of charge. Constructing real-space Wannier projections of Kohn-Sham orbitals based on the low-energy subspace of Mn $3d$ states and solving a multi-impurity problem, our approach focuses on local correlations at Mn sites. The antiferromagnetic insulating state in LiMnO${}_2$ has a moderate Néel temperature of $T_N=296K$ in agreement with experimental studies. Upon delithiation the system proceeds through a number of states: ferrimagnetic correlated metals at $x$=0.92, 0.83; multiple charge disproportionated ferromagnetic correlated metals with large quasiparticle weights at $x$=0.67, 0.50, 0.33; ferromagnetic metals with small quasiparticle weights at $x$=0.17, 0.08 and an antiferromagnetic insulator for the fully delithiated state, $x=0.0$. At moderate states of charge, $x=0.67-0.33$, a mix of +3/+4 formal oxidation states of Mn is observed, while the overall nominal oxidation of Mn state changes from +3 in LiMnO${}_2$ to +4 in MnO${}_2$. In all these cases the high-spin state emerges as the most likely state in our calculations considering the full $d$~manifold of Mn based on the proximity of $e_g$ levels in energy to $t_{2g}$. The quasiparticle peaks in the correlated metallic states were attributed to polaronic states based on previous literature for similar isoelectronic JT driven materials, arising due to non-Fermi liquid type behaviour of the strongly correlated system.

References in corpus (13)

• Hybridization expansion impurity solver: General formulation and application to Kondo lattice and two-orbital models
• Dynamical Mean-Field Theory within an Augmented Plane-Wave Framework: Assessing Electronic Correlations in the Iron Pnictide LaFeAsO
• Spin freezing transition and non-Fermi-liquid self-energy in a 3-orbital model
• Ab initio theory of polarons: formalism and applications
• Polarons from first principles, without supercells
• Pressure-induced metal-insulator transition in LaMnO3 is not of Mott-Hubbard type
• The low-energy ARPES and heat capacity of Na${}_{0.3}$CoO${}_2$: A DMFT study
• Localization of strongly correlated electrons as Jahn-Teller polarons in manganites
• Doping-driven Mott transition in La_{1-x}Sr_xTiO_3 via simultaneous electron and hole doping of t2g subbands
• Effects of Disorder on the Pressure-Induced Mott Transition in $\kappa$-BEDT-TTF)${}_2$Cu[N(CN)${}_2$]Cl
• Electronic Structure of LiMnO${}_2$: A Comparative Study of the LSDA and LSDA+U methods
• Effect of geometry on magnetism of Hund's metals: A case study with BaRuO${}_3$
• Understanding the role of exchange and correlations in complex oxides under strain and oxide heterostructures

Cited by in corpus (1)

• Decoupling the effects of geometry and nature of strain in LaMnO${}_3$: Interplay of dynamic correlations and uniaxial strain driving magnetic phase transitions