TY - UNPB
T1 - The importance of electronic correlations in exploring the exotic phase diagram of layered LixMnO2
AU - Banerjee, Hrishit
AU - Grey, Clare P.
AU - Morris, Andrew J.
PY - 2023/4/13
Y1 - 2023/4/13
N2 - Using ab initio dynamical mean-field theory we explore the electronic and magnetic states of layered LixMnO2 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 LiMnO2 has a moderate Néel temperature of TN=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 LiMnO2 to +4 in MnO2. 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 eg levels in energy to t2g. 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.
AB - Using ab initio dynamical mean-field theory we explore the electronic and magnetic states of layered LixMnO2 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 LiMnO2 has a moderate Néel temperature of TN=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 LiMnO2 to +4 in MnO2. 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 eg levels in energy to t2g. 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.
U2 - 10.48550/arXiv.2209.14682
DO - 10.48550/arXiv.2209.14682
M3 - Preprint
BT - The importance of electronic correlations in exploring the exotic phase diagram of layered LixMnO2
PB - arXiv
ER -