On-site Coulomb Interaction Research Articles

Oxygen and Electron Storage Effects in W-Modified Ceria Catalysts for Ammonia Conversion.

Tungsten-modified CeO2 is an excellent catalyst for the catalytic conversion of ammonia. However, the geometric and electronic properties of this catalyst and the detailed reaction mechanisms are not well understood. In this work, the potential configurations of various monomer tungsten oxides supported on the CeO2(111) surface (WOX(x=0-4)/CeO2(111)) are systematically studied and their relative stabilities are evaluated by using on-site Coulomb interaction corrected density functional theory calculations. Their performances are also investigated in enhancing the catalytic efficiency of NH3 adsorption and activation. It is found that the WOx clusters can always form tetrahedron-like structures on the CeO2(111) surface, and the CeO2(111) can exhibit both oxygen- and electron-storage roles to help the WOX maintain such tetrahedron-like WO4 structures and keep the W species at the highest 6+ state. Moreover, the flexibility of the tetrahedral WO4 structure leads to the preferential heterolytic NH3 dissociation at the WO sites, forming stable WNH2 and OH species. This study deepens the understanding of the unique oxygen- and electron-storage effects of the CeO2 support, it also provides valuable insights into the extraordinary catalytic properties of the W-modified CeO2 in NH3 conversion, paving the way for the rational design of more efficient CeO2-based NH3 treatment catalysts.

Pairing correlation of the kagome-lattice Hubbard model with the nearest-neighbor interaction

Abstract A recently discovered family of kagome lattice materials, AV3Sb5 (A = K,Rb,Cs), has attracted great interest, especially in the debate over their dominant superconducting pairing symmetry. To explore this issue, we study the superconducting pairing behavior within the kagome-lattice Hubbard model through the constrained path Monte Carlo method. It is found that doping around the Dirac point generates a dominant next-nearest-neighbor-d pairing symmetry driven by on-site Coulomb interaction U. However, when considering the nearest-neighbor interaction V, it may induce nearest-neighbor-p pairing to become the preferred pairing symmetry. Our results provide useful information to identify the dominant superconducting pairing symmetry in the AV3Sb5 family.

Large anomalous Nernst conductivity of L10-ordered CoPt in CoPt composition-spread thin films

We demonstrate a high-throughput experimental characterization of anomalous Nernst conductivity ( αxyA ) of L10-ordered CoPt using Co1–x Pt x composition-spread thin films on MgO(100) substrates. The compositional dependence of the anomalous Nernst effect, anomalous Hall effect (AHE) and Seebeck effect is systematically measured. As increasing the Pt concentration, the crystal structure in the composition-spread film grown at 500 °C changes from face-centered cubic (fcc) Co, A1-disordered CoPt, L10-ordered CoPt, A1-CoPt to fcc Pt. The largest αxyA of 2.52 A m–1 K–1 is obtained in L10-CoPt for Pt-rich composition of x = 70%, which is larger than that for an additionally fabricated nearly stoichiometric L10-Co48Pt52 reference uniform film. The contribution from direct conversion of a temperature gradient to a transverse charge current through αxyA is dominant to the total anomalous Nernst coefficient compared to the AHE-related contribution. From a scaling analysis of the AHE, the intrinsic contribution is found to be dominant for x = 70%. A theoretical calculation for αxyA of L10-Co50Pt50 agrees with the experimental αxyA value for the nearly stoichiometric reference film by considering on-site Coulomb interaction for Co atoms. We also point out the possible electron doping effect by the addition of Pt in L10-CoPt, which could explain the larger αxyA for the off-stoichiometric Pt-rich composition than that for the nearly stoichiometric one. Our experimental and theoretical results suggest the potential of L10-CoPt with a large αxyA originating from the intrinsic mechanism for future thermoelectric applications.

Mott-Insulator State of FeSe as a Van der Waals 2D Material Is Unveiled.

We undertook a comprehensive investigation of the electronic structure of FeSe, known as a Hund metal, and found that it is not uniquely defined. Through accounting for all two-particle irreducible diagrams constructed from electron Green's function G and screened Coulomb interaction W in a self-consistent manner, a Mott-insulator phase of 2D-FeSe is unveiled. The metal-insulator transition is driven by the strong on-site Coulomb interaction in its paramagnetic phase, accompanied by the weakening of both local and nonlocal screening effects on the Fe-3d orbitals. Our results suggest that Mott physics may play a pivotal role in shaping the electronic, optical, and superconducting properties of monolayer or nanostructured FeSe.

A DFT+U Study of the Structural and Electronic Properties of Zinc Doped Anatase TiO2 Nanomaterial

This work reports a theoretical study on the structural and electronic properties of the anatase phase of titanium dioxide (TiO2) within the framework of density functional theory corrected for on-site coulomb interactions in strongly correlated materials (DFT+U). The exchange correlation was described by local density approximation (LDA). The optimized lattice parameters obtained for the pure anatase TiO2 agree with the experimental data. Our results revealed that, after the zinc doping, the structure didn't change but there was a little expansion in the volume of the pure material. It was found that the doped structure's stability increases as the concentration of the dopant increases, but all the doped structures are stable. However, introducing the zinc dopant has significantly reduced the band gap of the pure anatase by 80.7 %, 80 %, and 78.6 % due to 0.25, 0.5, and 0.75 doping concentrations, respectively. This implies that the band gap energy increases as the doping concentration increases.

Magnetism and finite-temperature effects in UZr2: A density functional theory analysis

The structure and the thermophysical properties of δ-UZr2 are investigated using 0 K density functional theory and ab initio molecular dynamics (AIMD). Modeling the true paramagnetic state of this intermetallic compound has been challenging using first-principles calculations. For the first time, we find that the generalized gradient approximation method without applying an on-site Coulomb interaction term (Hubbard U) can result in a ground state that is antiferromagnetic (AFM). We believe that this weak AFM ground state is the closest to the real paramagnetic state. We found that structure optimization at finite temperatures using AIMD is necessary to achieve this ground state instead of the non-magnetic and ferromagnetic states previously reported in the literature. Our findings indicate that applying the Hubbard U on uranium f-orbitals in this metallic system is unnecessary and not recommended, as it leads to a large overestimation of the volume and introduces an unphysical strong spin polarization. Our approach results in atomic volume, thermal expansion, and heat capacities that have strong agreement with experiments.

Colossal Magnetoresistive Switching Induced by d0 Ferromagnetism of MgO in a Semiconductor Nanochannel Device with Ferromagnetic Fe/MgO Electrodes.

Exploring potential spintronic functionalities in resistive switching (RS) devices is of great interest for creating new applications, such as multifunctional resistive random-access memory and novel neuromorphic computing devices. In particular, the importance of the spin-triplet state of cation vacancies in oxide materials, which is induced by localized and strong O-2p on-site Coulomb interactions, in RS devices has been overlooked. d0 ferromagnetism sometimes appears due to the spin-triplet state and ferromagnetic Zener's double exchange interactions between cation vacancies, which are occasionally strong enough to make nonmagnetic oxides ferromagnetic. Here, for the first time, anomalous and colossal magneto-RS (CMRS) with very high magnetic field dependence is demonstrated by utilizing an unconventional RS device composed of a Ge nanochannel with all-epitaxial single-crystalline Fe/MgO electrodes. The device shows colossal and unusual behavior as the threshold voltage and ON/OFF ratio strongly depend on a magnetic field, which is controllable with an applied voltage. This new phenomenon is attributed to the formation of d0 -ferromagnetic filaments by attractive Mg vacancies due to the spin-triplet states with ferromagnetic double exchange interactions and the ferromagnetic proximity effect of Fe on MgO. The findings will allow the development of energy-efficient CMRS devices with multifield susceptibility.

A setup for hard x-ray time-resolved resonant inelastic x-ray scattering at SwissFEL.

We present a new setup for resonant inelastic hard x-ray scattering at the Bernina beamline of SwissFEL with energy, momentum, and temporal resolution. The compact R = 0.5 m Johann-type spectrometer can be equipped with up to three crystal analyzers and allows efficient collection of RIXS spectra. Optical pumping for time-resolved studies can be realized with a broad span of optical wavelengths. We demonstrate the performance of the setup at an overall ∼180 meV resolution in a study of ground-state and photoexcited (at 400 nm) honeycomb 5d iridate α-Li2IrO3. Steady-state RIXS spectra at the iridium L3-edge (11.214 keV) have been collected and are in very good agreement with data collected at synchrotrons. The time-resolved RIXS transients exhibit changes in the energy loss region <2 eV, whose features mostly result from the hopping nature of 5d electrons in the honeycomb lattice. These changes are ascribed to modulations of the Ir-to-Ir inter-site transition scattering efficiency, which we associate to a transient screening of the on-site Coulomb interaction.

Persistent current in a mesoscopic Holstein-Hubbard ring with Dresselhaus interaction

The effect of electron-phonon coupling, onsite repulsive Coulomb interaction and temperature on the persistent current in a quantum ring is studied in the presence of Dresselhaus spin-orbit interaction. The quantum ring threaded by the Aharonov-Bohm flux is modelled by the one-dimensional Holstein-Hubbard-Dresselhaus Hamiltonian. The electron-phonon interaction and Dresselhaus spin-orbit interaction are decoupled by employing the Lang-Firsov coherent transformation and a unitary transformation respectively. Thereafter, a self-consistent diagonalization technique is performed numerically at the Hartree-Fock level to obtain the effective electronic energy and current. It is shown that the intrinsic Dresselhaus spin-orbit interaction enhances the persistent charge and spin currents significantly. On the other hand, the persistent current is reduced by the onsite and nearest-neighbour electron-phonon interaction and Coulomb interaction. Also, the behaviour of the currents is modified by temperature. The spin-splitting of persistent spin current is enhanced considerably by Dresselhaus spin-orbit interaction and this splitting is tuneable in different regimes of magnetic flux, temperature, chemical potential and the interactions present in the system.

Polar NaTaO3/LaAlO3 (001) superlattices: A comparison of PBEsol and PBEsol+[formula omitted] first-principles calculations

The increasing experimental and theoretical interest in two-dimensional charge carrier gases formed at the interfaces of heterostructured perovskite oxide systems has led to a demand for a deeper understanding regarding the influence of exchange–correlation functionals and associated corrections on the systems’ properties. Herein, we investigate the impact of implementing additive Hubbard corrections compared to standard DFT routines using the PBEsol functional in polar NaTaO3/LaAlO3 (001) superlattices. Structural analysis reveals that the qualitative assessment remains consistent regardless of the approach, with slight variations observed for the NaTaO3 phase due to more pronounced polar distortions. Electronically, standard PBEsol fails to accurately describe the electronic structure of the superlattice below the system’s critical thickness, whereas the inclusion of on-site Coulomb interactions through PBEsol+U routines provides the correct semiconductor character of the superlattice, emphasizing the role of strong correlation effects on d and f electrons at the material’s interface. Additionally, our investigation reveals the spatial charge separation in the semiconductor heterostructure, with potential implications for photocatalytic devices. This work not only contributes to demonstrate the importance of the chosen methodology when studying such systems but also sheds light on important electronic and structural properties of NaTaO3/LaAlO3 (001) superlattices, enabling new avenues for future applications.

First-principle study of the electronic structure of layered Cu2Se

Copper selenide (Cu2Se) has attracted significant attention due to the extensive applications in thermoelectric and optoelectronic devices over the last few decades. Among various phase structures of Cu2Se, layered Cu2Se exhibits unique properties, such as purely thermal phase transition, high carrier mobility, high optical absorbance and high photoconductivity. Herein, we carry out a systematic investigation for the electronic structures of layered Cu2Se with several exchange-correlation functionals at different levels through first-principle calculations. It can be found that the electronic structures of layered Cu2Se are highly sensitive to the choice of functionals, and the correction of on-site Coulomb interaction also has a noticeable influence. Comparing with the results calculated with hybrid functional and G0W0method, it is found that the electronic structures calculated with LDA + U functional are relatively accurate for layered Cu2Se. In addition, the in-plane biaxial strain can lead to the transition of electronic properties from metal to semiconductor in the layered Cu2Se, attributed to the change of atomic orbital hybridization. Furthermore, we explore the spin-orbit coupling (SOC) effect of Cu2Se and find that the weak SOC effect on electronic structures mainly results from spatial inversion symmetry of Cu2Se. These findings provide valuable insights for further investigation on this compound.

Doubly Screened Coulomb Correction Approach for Strongly Correlated Systems.

Strongly correlated systems containing d/f electrons present a challenge to conventional density functional theory such as the local density approximation or generalized gradient approximation. We developed a doubly screened Coulomb correction (DSCC) approach to perform on-site Coulomb interaction correction for strongly correlated materials. The on-site Coulomb interaction between localized d/f electrons is self-consistently determined from a model dielectric function that includes both the static dielectric and Thomas-Fermi screening. We applied DSCC to simulate the electronic and magnetic properties of typical 3d, 4f, and 5f strongly correlated systems. The accuracy of DSCC is comparable to that of hybrid functionals but an order of magnitude faster. In addition, DSCC can reflect the difference in the Coulomb interaction between metallic and insulating situations, similar to the popular but computationally expensive constrained random phase approximation approach. This feature suggests that DSCC is also a promising method for simulating Coulomb interaction parameters.

Observation of Electronic Strong Correlation in VTe_{2}-2sqrt[3]×2sqrt[3] Monolayer.

Strong electron correlation under two-dimensional limit is intensely studied in the transition metal dichalcogenides monolayers, mostly within their charge density wave (CDW) states that host a star of David period. Here, by using scanning tunneling microscopy and spectroscopy and density functional theory calculations with on-site Hubbard corrections, we study the VTe_{2} monolayer with a different 2sqrt[3]×2sqrt[3] CDW period. We find that the dimerization of neighboring Te-Te and V-V atoms occurs during the CDW transition, and that the strong correlation effect opens a Mott-like full gap at Fermi energy (E_{F}). We further demonstrate that such a Mott phenomenon is ascribed to the combination of the CDW transition and on-site Coulomb interactions. Our work provides a new platform for exploring Mott physics in 2D materials.

Comprehensive AbInitio Investigation of the Phase Diagram of Quasi-One-Dimensional Molecular Solids.

An abinitio investigation of the family of molecular compounds TM_{2}X is conducted, where TM is either TMTSF or TMTTF and X takes centrosymmetric monovalent anions. By deriving the extended Hubbard-type Hamiltonians from first-principles band calculations and evaluating not only the intermolecular transfer integrals but also the Coulomb parameters, we discuss their material dependence in the unified phase diagram. Furthermore, we apply the many-variable variational MonteCarlo method to accurately determine the symmetry-breaking phase transitions, and show the development of the charge and spin orderings. We show that the material-dependent parameter can be taken as the correlation effect, represented by the value of the screened on-site Coulomb interaction U relative to the intrachain transfer integrals, for the comprehensive understanding of the spin and charge ordering in this system.

Dynamical approach to the atomic and electronic structures of the ductile semiconductor Ag2S.

Silver sulfide in monoclinic phase (α-Ag2S) has attracted significant attention owing to its metal-like ductility and promising thermoelectric properties near room temperature. However, first-principles studies on this material by density functional theory calculations have been challenging as both the symmetry and atomic structure of α-Ag2S predicted from such calculations are inconsistent with experimental findings. Here, we propose that a dynamical approach is imperative for correctly describing the structure of α-Ag2S. The approach is based on a combination of abinitio molecular dynamics simulation and deliberately chosen density functional considering both proper treatment of the van der Waals interaction and on-site Coulomb interaction. The obtained lattice parameters and atomic site occupations of α-Ag2S are in good agreement with experimental data. A stable phonon spectrum at room temperature can be obtained from this structure, which also yields a bandgap in accord with experimental measurements. The dynamical approach thus paves the way for studying this important ductile semiconductor in not only thermoelectric but also optoelectronic applications.

Spectral Signatures of a Negative Polaron in a Doped Polymer Semiconductor: Energy Levels and Hubbard U Interactions.

The modern picture of negative charge carriers on conjugated polymers invokes the formation of a singly occupied (spin-up/spin-down) level within the polymer gap and a corresponding unoccupied level above the polymer conduction band edge. The energy splitting between these sublevels is related to on-site Coulomb interactions between electrons, commonly termed Hubbard U. However, spectral evidence for both sublevels and experimental access to the U value is still missing. Here, we provide evidence by n-doping the polymer P(NDI2OD-T2) with [RhCp*Cp]2, [N-DMBI]2, and cesium. Changes in the electronic structure after doping are studied with ultraviolet photoelectron and low-energy inverse photoemission spectroscopies (UPS, LEIPES). UPS data show an additional density of states (DOS) in the former empty polymer gap while LEIPES data show an additional DOS above the conduction band edge. These DOS are assigned to the singly occupied and unoccupied sublevels, allowing determination of a U value of ∼1 eV.

Quantum Monte Carlo study of superconductivity in rhombohedral trilayer graphene under an electric field

By using the constrained-phase quantum Monte Carlo method, we performed a systematic study of the ground state of the half filled Hubbard model for a trilayer honeycomb lattice. We analyze the effect of the perpendicular electric field on the electronic structure, magnetic property, and pairing correlations. It is found that the antiferromagnetism is suppressed by the perpendicular electric field, especially the long-range parts, and the dominant magnetic fluctuations are still antiferromagnetic. The electronic correlation drives a $d+id$ superconducting pairing to be dominant over other pairing patterns among various electric fields and interaction strengths. We also found that the $d+id$ pairing correlation is greatly enhanced as the on-site Coulomb interaction is increased. Our intensive numerical results may unveil the nature of the recently observed superconductivity in rhombohedral trilayer graphene under an electric field.

Substitution effect on the electronic structure, magnetic anisotropy and thermoelectric behavior of Heusler-type Co[formula omitted]Mn[formula omitted]X[formula omitted]Si (X = V, Cr, Fe; 0[formula omitted]z[formula omitted]1) compounds: A density functional study

Here we explore the effect of partial substitution by transition-metal elements on the elastic, electronic, magnetic and thermoelectric properties of Heusler-type alloys Co2Mn1−zXzSi (X = V, Cr, and Fe; 0≤z≤1), within the framework of density functional theory (DFT). Although the optimized structures at z = 0.5 crystallize in tetragonal with space group P4/mmm, incorporation of the on-site Coulomb interaction (U) allows for a wider direct bandgap in the minority-spin channel for all the ternary and quaternary Heusler alloy compounds (HACs) leading to half-metallicity. The enthalpy of formation along with our estimate of elastic constants further reveals that all the HACs under study can remain stable thermodynamically even with a considerable amount of substitutional defects. Compared to other systems, Co2Mn0.25V0.75Si displays rather a high Poisson’s ratio of 0.36, indicating its ductile profile with the Vickers hardness of ∼ 3. We find that the ternary and quaternary HACs can retain the half-metallic (HM) character for the minority-spin channels with conduction band minima due to Co-d orbitals. Bandgap tuning has also been observed in Co2Mn1−zXzSi with X = V/Cr at z = 0.5, signifying how the substitutional defects can influence the electronic structure of HACs. The tetragonal structures (c/a≠ 1) at z = 0.5 are found to display higher in-plane magnetocrystalline anisotropy energy (e.g. MAE ∼70μeV, for X = V) than the cubic structures (c/a = 1) where it ceases eventually. This implies a strong dependence of MAE on the axial ratio, which can be tuned by way of uniaxial strain. The figure-of-merit analysis subsequently predicts Co2Mn0.25X0.75Si to possess better thermoelectric properties, especially with X = V/Cr. Such myriad abilities of HACs can potentially pave the way for designing better electrode materials in spintronic devices to generate controlled spin currents with resistance to high mechanical strain.

Quench dynamics in the one-dimensional mass-imbalanced ionic Hubbard model

Using the time-dependent Lanczos method, we study the nonequilibrium dynamics of the one-dimensional ionic-mass imbalanced Hubbard chain driven by a quantum quench of the on-site Coulomb interaction, where the system is prepared in the ground state of the Hamiltonian with a different Hubbard interaction. The exact diagonalization method (Lanczos algorithm) is adopted to study the zero temperature phase diagram in equilibrium, which is shown to be in good agreement with previous studies using density matrix renormalization group (DMRG). We then study the nonequilibrium quench dynamics of the spin and charge order parameters by fixing the initial and final Coulomb interactions while changing the quenching time protocols. Our study shows that the time evolution of the charge and spin order parameters strongly depend on the quenching time protocols. In particular, the effective temperature of the system will decrease monotonically as the quenching time is increased. By taking the final Coulomb interaction strength to be in the strong coupling regime, we find that the oscillation frequency of the charge order parameter increases monotonically with the Coulomb interaction. By contrast, the frequency of the spin order parameter decreases monotonically with increasing Coulomb interaction. We explain this result using an effective spin model and a two-site Hubbard model in the strong coupling limit. Finally, we take the final Coulomb interaction strength to be in the weak coupling regime and find that the oscillation frequency of both the charge and spin order parameters increases monotonically with decreasing Coulomb interaction. Our study suggests strategies to engineer the relaxation behavior of interacting quantum many-particle systems.

Evidence of charge susceptibility and multiple f–c hybridization configurations with the La doping in CeGe: a DFT + DMFT study

Kondo coupling has been extensively investigated in several Ce-based systems. However, the search for materials showing the interplay between the Kondo effect, spin–orbit interaction, and crystal-field effect along with the presence of local charge susceptibility; remains a challenge for the condensed matter community. Actually, in Ce-based systems, the strong coupling of the conduction electrons to the local magnetic moments usually hides these properties. Here, we present a detailed investigation of Ce0.6La0.4Ge through a combined density functional theory and dynamic mean-field theory study. Our investigations give evidence of the significant charge susceptibility and the multiple different f–c hybridization configurations. The weakening of the magnetization owing to the dilution of the Ce-site is the main cause for the appearance of such properties, which is believed to occur due to the presence of the relevant local moment and f–c hybridization over the competition with the on-site Coulomb interaction.