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Register a new userUnusual Mott transition associated with charge-order melting in BiNiO$_3$ under pressure
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We study the electronic structure, magnetic state, and phase stability of paramagnetic BiNiO$_3$ near a pressure-induced Mott insulator-to-metal transition (MIT) by employing a combination of density functional and dynamical mean-field theory. We obtain that BiNiO$_3$ exhibits an anomalous negative-charge-transfer insulating state, characterized by charge disproportionation of the Bi $6s$ states, with Ni$^{2+}$ ions. Upon a compression of the lattice volume by $sim$4.8%, BiNiO$_3$ is found to make a Mott MIT, accompanied by the change of crystal structure from triclinic $Pbar{1}$ to orthorhombic $Pbnm$. The pressure-induced MIT is associated with the melting of charge disproportionation of the Bi ions, caused by a charge transfer between the Bi $6s$ and O $2p$ states. The Ni sites remain to be Ni$^{2+}$ across the MIT, which is incompatible with the valence-skipping Ni$^{2+}$/Ni$^{3+}$ model. Our results suggest that the pressure-induced change of the crystal structure drives the MIT in BiNiO$_3$.
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We present a computational study of PbCoO$_3$ at ambient and elevated pressure. We employ the static and dynamic treatment of local correlation in form of density functional theory + $U$ (DFT+$U$) and + dynamical mean-field theory (DFT+DMFT). Our results capture the experimentally observed crystal structures and identify the unsaturated Pb $6s$ - O $2p$ bonds as the driving force beyond the complex physics of PbCoO$_3$. We provide a geometrical analysis of the structural distortions and discuss their implications, in particular, the internal doping, which triggers transition between phases with and without local moments and a site selective Mott transition in the low-pressure phase.
We compute the electronic structure, spin and charge state of Fe ions, and structural phase stability of paramagnetic CaFeO$_3$ under pressure using a fully self-consistent in charge density DFT+dynamical mean-field theory method. We show that at ambient pressure CaFeO$_3$ is a negative charge-transfer insulator characterized by strong localization of the Fe $3d$ electrons. It crystallizes in the monoclinic $P2_1/n$ crystal structure with a cooperative breathing mode distortion of the lattice. While the Fe $3d$ Wannier occupations and local moments are consistent with robust charge disproportionation of Fe ions in the insulating $P2_1/n$ phase, the physical charge density difference around the structurally distinct Fe A and Fe B ions with the ``contracted and ``expanded oxygen octahedra, respectively, is rather weak, $sim$0.04. This implies the importance of the Fe $3d$ and O $2p$ negative charge transfer and supports the formation of a bond-disproportionated state characterized by the Fe A $3d^{5-delta}underline{L}^{2-delta}$ and Fe B $3d^5$ valence configurations with $delta ll 1$, in agreement with strong hybridization between the Fe $3d$ and O $2p$ states. Upon compression above $sim$41 GPa CaFeO$_3$ undergoes the insulator-to-metal phase transition (IMT) which is accompanied by a structural transformation into the orthorhombic $Pbnm$ phase. The phase transition is accompanied by suppression of the cooperative breathing mode distortion of the lattice and, hence, results in the melting of bond disproportionation of the Fe ions. Our analysis suggests that the IMT transition is associated with orbital-dependent delocalization of the Fe $3d$ electrons and leads to a remarkable collapse of the local magnetic moments. Our results imply the crucial importance of the interplay of electronic correlations and structural effects to explain the properties of CaFeO$_3$.
The electronic structure, magnetic moment, and volume collapse of MnO under pressure are obtained from four different correlated band theory methods; local density approximation + Hubbard U (LDA+U), pseudopotential self-interaction correction (pseudo-SIC), the hybrid functional (combined local exchange plus Hartree-Fock exchange), and the local spin density SIC (SIC-LSD) method. Each method treats correlation among the five Mn 3d orbitals (per spin), including their hybridization with three O $2p$ orbitals in the valence bands and their changes with pressure. The focus is on comparison of the methods for rocksalt MnO (neglecting the observed transition to the NiAs structure in the 90-100 GPa range). Each method predicts a first-order volume collapse, but with variation in the predicted volume and critical pressure. Accompanying the volume collapse is a moment collapse, which for all methods is from high-spin to low-spin (5/2 to 1/2), not to nonmagnetic as the simplest scenario would have. The specific manner in which the transition occurs varies considerably among the methods: pseudo-SIC and SIC-LSD give insulator-to-metal, while LDA+U gives insulator-to-insulator and the hybrid method gives an insulator-to-semimetal transition. Projected densities of states above and below the transition are presented for each of the methods and used to analyze the character of each transition. In some cases the rhombohedral symmetry of the antiferromagnetically ordered phase clearly influences the character of the transition.
The pressure-induced insulator to metal transition (IMT) of layered magnetic nickel phosphorous tri-sulfide NiPS3 was studied in-situ under quasi-uniaxial conditions by means of electrical resistance (R) and X-ray diffraction (XRD) measurements. This sluggish transition is shown to occur at 35 GPa. Transport measurements show no evidence of superconductivity to the lowest measured temperature (~ 2 K). The structure results presented here differ from earlier in-situ work that subjected the sample to a different pressure state, suggesting that in NiPS3 the phase stability fields are highly dependent on strain. It is suggested that careful control of the strain is essential when studying the electronic and magnetic properties of layered van der Waals solids.
We have measured the reflectivity spectra of the barium iridate $9R$ BaIrO$_3$, the crystal structure of which consists of characteristic Ir$_3$O$_{12}$ trimers. In the high-temperature phase above the transition temperature $T_csimeq180$ K, we find that the optical conductivity involves two temperature-dependent optical transitions with an ill-defined Drude response. These features are reminiscent of the optical spectra in the organic dimer Mott insulators, implying a possible emergence of an unusual electronic state named trimer Mott insulator in BaIrO$_3$, where the carrier is localized on the trimer owing to the strong Coulomb repulsion. Along with a pronounced splitting of the phonon peak observed below $T_c$, which is a hallmark of charge disproportionation, we discuss a possible phase transition from the trimer Mott insulator to a charge-ordered insulating phase in BaIrO$_3$.
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