Mean-field Theory Calculations Research Articles

Charge Self-consistent Dynamical Mean Field Theory Calculations in Combination with Linear Combination of Numerical Atomic Orbitals Framework based Density Functional Theory

Charge Self-consistent Dynamical Mean Field Theory Calculations in Combination with Linear Combination of Numerical Atomic Orbitals Framework based Density Functional Theory

Quantifying the U 5f covalence and degree of localization in U intermetallics

A procedure for quantifying the U 5f electronic covalency and degree of localization in U intermetallic compounds is presented. To this end, bulk sensitive hard and soft x-ray photoelectron spectroscopy were utilized in combination with density-functional theory (DFT) plus dynamical mean-field theory (DMFT) calculations. The energy dependence of the photoionization cross sections allows the disentanglement of the U 5f contribution to the valence band from the various other atomic subshells so the computational parameters in the DFT+DMFT can be reliably determined. Applying this method to UGa2 and UB2 as model compounds from opposite ends of the (de)localization range, we have achieved excellent simulations of the valence band and core-level spectra. The width in the distribution of atomic U 5f configurations contributing to the ground state, as obtained from the calculations, quantifies the correlated nature and degree of localization of the U 5f. The findings permit answering the longstanding question why different spectroscopic techniques give seemingly different numbers for the U 5f valence in intermetallic U compounds. Published by the American Physical Society 2024

Ab-initio DFT＋[formula omitted] study on the electronic correlation in multiferroic XY-antiferromagnetic Ba2CoGe2O7

Ab-initio density functional theory (DFT)＋U has been used to study the spin-resolved electronic band structure and the partial density of states of the multiferroic XY-antiferromagnetic Ba2CoGe2O7. Using the constrained random-phase approximation (cRPA) method, the value of Hubbard U and Hund’s coupling JH has been determined and plugged into the further dynamical mean field theory (DMFT) calculations. The strong metal-ligand hybridization between Co-3d and O-2p orbitals in the CoO4 tetrahedron has been demonstrated via DFT and DFT＋DMFT calculations. The calculated indirect band gap in the antiferromagnetic state without and with U (=5 eV) correction is found to be 0.67 and 2.71 eV, respectively. The highest calculated ordered magnetic moment of 2.7 μB/Co2+ is close to the reported experimental value. The presented DFT calculations based on the different orbital models brings the underlying strong electronic correlation in the Ba2CoGe2O7.

Orbital selectivity in Sn adatom adlayer on a Si(111) surface

Unconventional quantum many-particle phenomenon naturally emerges when approaching the Mott-Hubbard insulating state. Finding insulator-metal transition in correlated adatoms in semiconductor surfaces provides an ideal material platform to design electronic states which may host superconductivity in two-dimensional electron systems. To uncover the microscopics underlying by multi-orbital interactions, we perform density functional plus dynamical mean-field theory calculations for the all-electron Hubbard model, unraveling a Mott assisted Kondo insulating state in the atomic Sn layer deposited onto a Si(111) surface, also referred to as α-Sn. We propose that α-Sn is an ideal testing ground to explore hidden orbital selectivity and pseudogap behavior all arising from Mottness and discuss the relevance of our results for pure and hole-doped α-Sn in the context of spectroscopy and tunnelling experiments of adatom lattices.

The Mott transition in the 5d[formula omitted] compound Ba[formula omitted]NaOsO[formula omitted]: A DFT+DMFT study with PAW spinor projectors

Spin–orbit coupling has been reported to be responsible for the insulating nature of the 5d1 osmate double perovskite Ba2NaOsO6 (BNOO). However, whether spin–orbit coupling indeed drives the metal-to-insulator transition (MIT) in this compound is an open question. In this work we investigate the impact of relativistic effects on the electronic properties of BNOO via density functional theory plus dynamical mean-field theory calculations in the paramagnetic regime, where the insulating phase is experimentally observed. The correlated subspace is modeled with spinor projectors of the projector augmented wave method (PAW) employed in the Vienna Ab Initio Simulation Package (VASP), suitably interfaced with the TRIQS package. The inclusion of PAW spinor projectors in TRIQS enables the treatment of spin–orbit coupling effects fully ab-initio within the dynamical mean-field theory framework. In the present work, we show that spin–orbit coupling, although assisting the MIT in BNOO, is not the main driving force for its gapped spectra, placing this material in the Mott insulator regime. Relativistic effects primarily impact the correlated states’ character, excitations, and magnetic ground-state properties.

Oxygen Hole Formation Controls Stability in LiNiO2 Cathodes: DFT Studies of Oxygen Loss and Singlet Oxygen Formation in Li-Ion Batteries

Ni-rich cathode materials achieve both high voltages and capacities in Li-ion batteries but are prone to structural instabilities and oxygen loss via the formation of singlet oxygen. Using ab initio molecular dynamics simulations, we observe spontaneous O2 loss from the (012) surface of delithiated LiNiO2, singlet oxygen forming in the process. We find that the origin of the instability lies in the pronounced oxidation of O during delithiation, i.e., O plays a central role in Ni-O redox in LiNiO2. For LiNiO2, NiO2, and the prototype rock salt NiO, density-functional theory and dynamical mean-field theory calculations based on maximally localised Wannier functions yield a Ni charge state of ca. +2, with O varying between –2 (NiO), –1.5 (LiNiO2) and –1 (NiO2). Predicted XAS Ni K and O K-edge spectra are in excellent agreement with experimental XAS spectra, confirming the predicted charge states. The calculations also show that a high-voltage O K-edge feature at 531 eV previously assigned to lattice O-redox processes could alternatively arise from O-redox induced water intercalation and O–O dimer formation with lattice O at high states of charge. The O2 surface loss route observed here consists of 2 surface O•– radicals combining to form a peroxide ion, which is oxidised to O2, leaving behind 2 O vacancies and 2 O2– ions: effectively 4 O•– radicals disproportionate to O2 and 2 O2– ions. The reaction liberates ca. 3 eV per O2 molecule. Singlet oxygen formation is caused by the singlet ground state of the peroxide ion, with spin conservation dictating the preferential release of 1O2, the strongly exergonic reaction providing the free energy required for the formation of 1O2 in its excited state.

Fate of Quasiparticles at High Temperature in the Correlated Metal Sr_{2}RuO_{4}.

We study the temperature evolution of quasiparticles in the correlated metal Sr_{2}RuO_{4}. Our angle resolved photoemission data show that quasiparticles persist up to temperatures above 200K, far beyond the Fermi liquid regime. Extracting the quasiparticle self-energy, we demonstrate that the quasiparticle residue Z increases with increasing temperature. Quasiparticles eventually disappear on approaching the bad metal state of Sr_{2}RuO_{4} not by losing weight but via excessive broadening from super-Planckian scattering. We further show that the Fermi surface of Sr_{2}RuO_{4}-defined as the loci where the spectral function peaks-deflates with increasing temperature. These findings are in semiquantitative agreement with dynamical mean field theory calculations.

Orbital-selective metal skin induced by alkali-metal-dosing Mott-insulating Ca2RuO4

Doped Mott insulators are the starting point for interesting physics such as high temperature superconductivity and quantum spin liquids. For multi-band Mott insulators, orbital selective ground states have been envisioned. However, orbital selective metals and Mott insulators have been difficult to realize experimentally. Here we demonstrate by photoemission spectroscopy how Ca2RuO4, upon alkali-metal surface doping, develops a single-band metal skin. Our dynamical mean field theory calculations reveal that homogeneous electron doping of Ca2RuO4 results in a multi-band metal. All together, our results provide evidence for an orbital-selective Mott insulator breakdown, which is unachievable via simple electron doping. Supported by a cluster model and cluster perturbation theory calculations, we demonstrate a type of skin metal-insulator transition induced by surface dopants that orbital-selectively hybridize with the bulk Mott state and in turn produce coherent in-gap states.

Electromagnetic signatures of a chiral quantum spin liquid

Quantum spin liquids (QSL) have emerged as a captivating subject within interacting spin systems that exhibit no magnetic ordering even at the lowest temperature accessible experimentally. However, definitive experimental evidence remains elusive. In light of the recent surge in theoretical and experimental interest in the half-filled Hubbard model on a triangular lattice, which offers the potential for stabilizing a chiral QSL, we investigate the electromagnetic signatures of this phase to facilitate experimental detection. Utilizing a combination of parton mean-field theory and unbiased density-matrix renormalization group calculations, we systematically examine the electrical charge and orbital electrical current associated with a spinon excitation in the chiral QSL. Additionally, we calculate the longitudinal and transverse optical conductivities below the Mott gap. Furthermore, employing quantum field theory analysis, we unravel the connection between spinon excitations and emergent as well as physical gauge fields. Our results demonstrate that the chiral QSL phase exhibits a distinct electromagnetic response, even within a Mott insulator regime. This finding holds great potential for enabling the experimental detection of this long-sought-after phase.

Structural, electronic and magnetic properties of Fe-doped strontium ruthenates

By employing a combined approach of density-functional theory (DFT) and dynamical mean-field theory (DMFT) calculations, we examine the structural, electronic, and magnetic characteristics of two distinct strontium ruthenates: Sr2RuO4, an unconventional superconductor, and the correlated metal SrRuO3, both at 50% Fe-doping level. In both Sr2Fe0.5Ru0.5O4 and SrFe0.5Ru0.5O3, the original ruthenium (Ru) and the dopant iron (Fe) atoms adopt 3-dimensional and 2-dimensional G-type structures, respectively. The hybridization between Fe-3d and Ru-4d is comparatively weaker than in other double perovskite systems. The interplay between strong correlations and reduced itinerancy results in significant spin splitting at Fe and Ru sites. Consequently, a charge transfer process, along with the super-exchange effect, leads to antiferromagnetically coupled Fe3+ and Ru5+ ions and establishes a semiconducting ferrimagnetic order. Subsequent DMFT calculations demonstrate the persistence of the ferrimagnetic order even at room temperature (300 K). These findings align with prior reports on SrFe0.5Ru0.5O3, thus reinforcing the notion that 3d–4d transition metal oxides hold considerable promise as candidates for high-performance spintronic devices, such as spin-valve sensors and spintronic giant magnetoresistance devices.

Horizontal to perpendicular transition of lamellar and cylinder phases in block copolymer films induced by interface segregation of single-chain nanoparticles during solvent evaporation.

How to fabricate perpendicularly oriented domains (PODs) of lamellar and cylinder phases in block copolymer thin films remains a major challenge. In this work, via a coarse-grained molecular dynamics simulation study, we report a solvent evaporation strategy starting from a mixed solution of A-b-B-type diblock copolymers (DBCs) and single-chain nanoparticles (SCNPs) with the same composition, which is capable of spontaneously generating PODs in drying DBC films induced by the interface segregation of SCNPs. The latter occurs at both the free surface and substrate and, consequently, neutralizes the interface selectivity of distinct blocks in DBCs, leading to spontaneous formation of PODs at both interfaces. The interface segregation of SCNPs is related to the weak solvophilicity of the internal cross-linker units. A mean-field theory calculation demonstrates that the increase in the chemical potential of SCNPs in the bulk region drives their interface segregation along with solvent evaporation. We believe that such a strategy can be useful in regulating the PODs of DBC films in practical applications.

Probing Hidden Mott Gap and Incommensurate Charge Modulation on the Polar Surfaces of PdCrO_{2}.

Here we report a combined study of low-temperature scanning tunneling microscopy and dynamical mean-field theory on PdCrO_{2}, a delafossite metal with an antiferromagnetic order below ∼37.5 K. First, on the CrO_{2}-terminated polar surface we detect a gaplike feature both below and above the Néel temperature. The dynamical mean-field theory calculations indicate that this gap is opened due to the strong correlations of Cr-3d electrons, suggesting the hidden Mott nature of the gap. Then, we observe two kinds of Pd-terminated polar surfaces. One is a well-ordered Pd surface with the Fermi-surface-nesting-induced incommensurate charge modulation, while the other one is a reconstructed Pd surface with the individual nanoscale nonperiodic domain structures. On the well-ordered Pd surface, the interference between the incommensurate charge modulation and the atomic lattice forms the periodic moiré pattern. Our results provide important microscopic information for fully understanding the correlated electronic properties of this class of materials.

Heavy quasiparticles and cascades without symmetry breaking in twisted bilayer graphene

Among the variety of correlated states exhibited by twisted bilayer graphene, cascades in the spectroscopic properties and in the electronic compressibility occur over larger ranges of energy, twist angle and temperature compared to other effects. This suggests a hierarchy of phenomena. Using a combined dynamical mean-field theory and Hartree calculation, we show that the spectral weight reorganisation associated with the formation of local moments and heavy quasiparticles can explain the cascade of electronic resets without invoking symmetry breaking orders. The phenomena reproduced here include the cascade flow of spectral weight, the oscillations of remote band energies, and the asymmetric jumps of the inverse compressibility. We also predict a strong momentum differentiation in the incoherent spectral weight associated with the fragile topology of twisted bilayer graphene.

Role of electron correlation and disorder on the electronic structure of layered nickelate (La0.5Sr0.5)2NiO4

We investigate the role of electron correlation and disorder on the electronic structure of layered nickelate ${({\mathrm{La}}_{0.5}{\mathrm{Sr}}_{0.5})}_{2}{\mathrm{NiO}}_{4}$ using core level and valence band photoemission spectroscopy in conjunction with density functional theory (DFT) and dynamical mean-field theory (DMFT) calculations. Sr $3d$ and La $4d$ core level spectra exhibit multiple features associated with photoemission final-state effects. An increase of unscreened features in the Sr $3d$ and La $4d$ core level spectra with lowering temperature suggests the reduction in density of states (DOS) at the Fermi level, ${E}_{F}$. Valence band spectra collected using different photon energies reveal finite intensity at ${E}_{F}$ and overall spectra are well captured by $\mathrm{DFT}+\mathrm{DMFT}$. Strong renormalization of partially filled ${e}_{g}$ bands in $\mathrm{DFT}+\mathrm{DMFT}$ result indicates strong correlation in this system. Mass enhancement factor, ${m}^{*}/{m}_{\text{DFT}}\ensuremath{\sim}$ 3, agrees well with values obtained from specific heat measurements. High-resolution spectra in the vicinity of ${E}_{F}$ show monotonically decreasing spectral intensity with lowering temperature, which evolves to exhibit a Fermi cutoff at low temperatures indicating metallic character in contrast to insulating transport, suggesting Anderson insulating state. $|E\ensuremath{-}{E}_{F}{|}^{1/2}$ dependence of the spectral DOS and square-root temperature dependence of spectral DOS at ${E}_{F}$ evidences the role of disorder in the electronic structure of ${({\mathrm{La}}_{0.5}{\mathrm{Sr}}_{0.5})}_{2}{\mathrm{NiO}}_{4}$.

Experimental analysis of carbon-based Phase Change Materials composites for a fast numerical design of cold energy storage systems

The adoption of highly conductive nanofillers within a phase change material (PCM) matrix is considered a promising solution to enhance the effective thermal conductivity of the resulting nanocomposite, thus possibly increasing specific power and energy density in latent thermal energy storage plants. However, the expected significant property enhancement of such composite materials is often unmet, with one of the key reason being the critical and poorly studied role played by too high thermal resistances at the nanofiller-matrix interfaces limiting the heat flux within the material. One of the contributions of this work is providing an estimate of the value for such resistances in relevant cases for cold energy storage found to be in the range of: 3⋅10−7 - 3⋅10−6[m2K/W]. Those estimates have been obtained by exploiting a synergistic study combining a numerical analysis, based on mean-field theory calculations and finite element simulations, with experimental assessment of the resulting properties of nanocomposite samples. In addition, we show how the numerically predicted values of the effective thermal conductivity can be used as input data in an approximated numerical analysis of a lab-scale shell & tube storage tank connected to a daily domestic user, adopted for the storage of sub-ambient temperature thermal energy. This leads to a novel multi-scale analysis coupling the material effective properties and the expected behavior at the plant level, thus allowing a preliminary computationally efficient optimization of the storage system under analysis. Compared to computational fluid dynamics simulations, the approximated design approach proved to predict the propagation front up to 30% accuracy.

Low-rank Green's function representations applied to dynamical mean-field theory

Several recent works have introduced highly compact representations of single-particle Green's functions in the imaginary time and Matsubara frequency domains, as well as efficient interpolation grids used to recover the representations. In particular, the intermediate representation with sparse sampling and the discrete Lehmann representation (DLR) make use of low rank compression techniques to obtain optimal approximations with controllable accuracy. We consider the use of the DLR in dynamical mean-field theory (DMFT) calculations, and in particular show that the standard full Matsubara frequency grid can be replaced by the compact grid of DLR Matsubara frequency nodes. We test the performance of the method for a DMFT calculation of ${\mathrm{Sr}}_{2}{\mathrm{RuO}}_{4}$ at temperature $50\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ using a continuous-time quantum Monte Carlo impurity solver, and demonstrate that Matsubara frequency quantities can be represented on a grid of only 36 nodes with no reduction in accuracy, or increase in the number of self-consistent iterations, despite the presence of significant Monte Carlo noise.

Structure of the normal state and origin of the Schottky anomaly in the correlated heavy-fermion superconductor UTe2

The recently discovered $\mathrm{U}{\mathrm{Te}}_{2}$ superconductor is regarded as a heavy-fermion mixed-valence system with very peculiar properties within the normal and superconducting (SC) states. It shows no signs of magnetic order, but has a strong anisotropy of magnetic susceptibility and SC critical field. In addition to a heavy-fermion-like behavior in the normal state, it exhibits a distinctive Schottky-type anomaly at $\ensuremath{\sim}12$ K and a characteristic excitations gap $\ensuremath{\sim}35\ensuremath{-}40$ K. Here, we show, by virtue of dynamical mean-field theory calculations with a quasiatomic treatment of electron correlations, that ab initio-derived crystal-field splitting of the $5{f}^{2}$ ionic configuration yields agreement with these experimental observations. A close analogy of the normal paramagnetic state of $\mathrm{U}{\mathrm{Te}}_{2}$ to that of $\mathrm{U}{\mathrm{Ru}}_{2}{\mathrm{Si}}_{2}$ in the Kondo arrest scenario is revealed. We consider the impact of anisotropic superexchange interactions within the U-U structural dimer on magnetization and development of strong orbital and magnetic moment fluctuations in $\mathrm{U}{\mathrm{Te}}_{2}$.

Topological surface states and phase transition in BaTh2Fe4As4(N1−xOx)2 superconductors

We perform density functional theory and density functional theory plus dynamical mean-field theory calculations to study the electronic structures and topological properties of iron-based superconductors ${\mathrm{BaTh}}_{2}{\mathrm{Fe}}_{4}{\mathrm{As}}_{4}{({\mathrm{N}}_{1\ensuremath{-}x}{\mathrm{O}}_{x})}_{2}$ ($x=0.1$, 0.2, and 0.3). Taking into account electronic correlation corrections, we find that at small oxygen dopings ($x=0.1$ and 0.2), the ${\mathrm{BaTh}}_{2}{\mathrm{Fe}}_{4}{\mathrm{As}}_{4}{({\mathrm{N}}_{1\ensuremath{-}x}{\mathrm{O}}_{x})}_{2}$ superconductors have nontrivial band topology and Dirac-cone type topological surface states around the Fermi level on the (001) surface, which indicates that they can harbor Majorana zero modes on the (001) surface. Increasing the oxygen doping level, the ${\mathrm{BaTh}}_{2}{\mathrm{Fe}}_{4}{\mathrm{As}}_{4}{({\mathrm{N}}_{1\ensuremath{-}x}{\mathrm{O}}_{x})}_{2}$ superconductor undergoes a topological phase transition between $x=0.2$ and 0.3, and has trivial band topology and no topological surface states on the (001) surface at $x=0.3$. The coexistence of high-temperature superconductivity, topological surface states, and topological phase transition in ${\mathrm{BaTh}}_{2}{\mathrm{Fe}}_{4}{\mathrm{As}}_{4}{({\mathrm{N}}_{1\ensuremath{-}x}{\mathrm{O}}_{x})}_{2}$ superconductors makes them potential platforms to study topological superconductivity, Majorana zero modes and effects induced by a topological phase transition.

Metal–insulator transition in composition-tuned nickel oxide films

Thin films of the solid solution NdLaNiO3 are grown in order to study the expected 0 K phase transitions at a specific composition. We experimentally map out the structural, electronic and magnetic properties as a function of x and a discontinuous, possibly first order, insulator–metal transition is observed at low temperature when x = 0.2. Raman spectroscopy and scanning transmission electron microscopy show that this is not associated with a correspondingly discontinuous global structural change. On the other hand, results from density functional theory (DFT) and combined DFT and dynamical mean field theory calculations produce a 0 K first order transition at around this composition. We further estimate the temperature-dependence of the transition from thermodynamic considerations and find that a discontinuous insulator–metal transition can be reproduced theoretically and implies a narrow insulator–metal phase coexistence with x. Finally, muon spin rotation (µSR) measurements suggest that there are non-static magnetic moments in the system that may be understood in the context of the first order nature of the 0 K transition and its associated phase coexistence regime.

Collective Quantum Magnetism in Nitrogen-Doped Nanographenes.

The emergence of quantum magnetism in nanographenes provides ample opportunities to fabricate purely organic devices for spintronics and quantum information. Although heteroatom doping is a viable way to engineer the electronic properties of nanographenes, the synthesis of doped nanographenes with collective quantum magnetism remains elusive. Here, a set of nitrogen-doped nanographenes (N-NGs) with atomic precision are fabricated on Au(111) through a combination of imidazole [2+2+2]-cyclotrimerization and cyclodehydrogenation reactions. High-resolution scanning probe microscopy measurements reveal the presence of collective quantum magnetism for nanographenes with three radicals, with spectroscopic features which cannot be captured by mean-field density functional theory calculations but can be well reproduced by Heisenberg spin model calculations. In addition, the mechanism of magnetic exchange interaction of N-NGs has been revealed and compared with their counterparts with pure hydrocarbons. Our findings demonstrate the bottom-up synthesis of atomically precise N-NGs which can be utilized to fabricate low-dimensional extended graphene nanostructures for realizing ordered quantum phases.