Electron Correlation Effects Research Articles

Investigating the structural, electronic, and magnetic properties of Cd1-xVxTe: Insights from First-Principles calculations

In our study, we aim to investigate the structural, electronic, and magnetic properties of CdVTe, a diluted magnetic semiconductor with a Cadmium telluride (CdTe) structure. To achieve this, we employ the full potential linear augmented plane wave method implemented in the CASTEP code, which allows us to accurately simulate the behavior of the system. To describe the electronic exchange and correlation effects, we adopt the generalized gradient approximation (GGA) within the density functional theory (DFT) framework. This choice of methodology ensures reliable and accurate calculations of the electronic and magnetic properties of Cd1-xVxTe. Our results reveal that the substitution of Vanadium (V) into the Cadmium (Cd) site of the CdTe lattice does not alter the zinc blende crystal structure, demonstrating the stability and structural integrity of the system. Furthermore, our calculations demonstrate that the introduction of Vanadium impurities leads to spin polarization within the material, resulting in the emergence of a magnetic moment. Notably, we find that a Vanadium concentration of approximately x≈0.12 exhibits the strongest magnetic properties, characterized by a significant magnetic moment. These findings provide valuable insights into the behavior and potential applications of CdVTe as a diluted magnetic semiconductor, shedding light on the interplay between structural, electronic, and magnetic properties in this material.

The excitation energies and hyperfine structures for 2l, 3l states in lithiumlike ions

Combining the multi-configuration Dirac–Hartree–Fock method and the model-quantum electrodynamics (QED) approach, the wave functions, transition energies and hyperfine structure constants for 2l, 3l states in Li-like Ne7+, Mg9+, Al10+, P12+, Ar15+ and Ca17+ ions are calculated. The effects of electron correlation, Breit interactions, nuclear recoil and QED effects are analyzed in detail. We find that the contribution of the non-diagonal elements of the self-energy is significant for the 2p1/2→2s1/2 and 2p3/2→2s1/2 transitions. However, for the 3l→2s1/2 transitions, the contribution of non-diagonal elements is small. The accuracy of the currently calculated hyperfine structure constants is expected to be within 1%.

Toward Direct Exploration of the Few-Femtosecond Dynamics of Electronic Coherence and Correlation in Quantum Materials Using Time- and Angle-Resolved Photoemission Spectroscopy

Over the last two decades, time- and angle-resolved photoemission spectroscopy (trARPES) has become a mature and established experimental technique for the study of ultrafast electronic and structural dynamics in materials. To date, most trARPES investigations have focused on the investigation of processes occurring on time scales of ≳30 fs, in particular, relaxation and thermalization, and have therefore been blind to the initial sub-10 fs dynamics related to electronic coherence and correlation effects. In this article, we illustrate how current trARPES setups reach their limits when it comes to addressing such extraordinarily short time scales and present an experimental configuration that provides the time, energy, and momentum resolutions required to monitor few-femtosecond dynamics on the relevant energy and momentum scales. We discuss the potential capabilities of such an experiment to study the electronic response of materials in the strong-field interaction regime at PHz frequencies and finally review a theoretical concept that may in the future even overcome the competing resolution limitations of trARPES experiments, as imposed by the time–bandwidth product of the probing laser pulse. Our roadmap for ultrafast trARPES indicates a path to break new experimental ground in quantum nonequilibrium electronic dynamics, from which new possibilities for ultrafast control of optical and electronic signals in quantum materials can be explored.

The Landé g factors of highly charged Sn47+ and Bi80+ ions

The wavefunctions and eigenvalues of the ground states of Sn47+, and Bi80+ ions are calculated using the fully relativistic multiconfiguration Dirac-Hartree–Fock (MCDHF) method. Detailed investigation are carried out to study the effects of electron correlation, Breit interaction, quantum electrodynamics (QED), and nuclear recoil. Based on these calculations, the theoretical predictions for the g factors of the ground states of Sn47+ and Bi80+ ions are 1.980429 and 1.934759, respectively. The accuracy of these calculations is expected to be on the order of 10−5.

Potential-Energy Curves for the Ground and Several Electronic States of NdO and NdS.

Potential energy curves (PECs) were calculated for 21 and 18 electronic states of NdO and NdS molecules, respectively. In each case, static electron correlation effects were described by incomplete model space multiconfiguration self-consistent field wave functions based on an active space that included the most important valence orbitals. Dynamic electron correlation was included by the multireference second-order generalized Van Vleck perturbation theory method. Scalar-relativistic contributions were included by the effective core potential approach, using def2-TZVPP basis sets. Spin-dependent relativistic corrections were determined to be small and negligible for the Nd atom and so were not included in the calculations. The 21 and 18 electronic states of NdO and NdS were predicted to be in the excitation energy range of ∼3.2 and ∼2.7 eV, respectively. The ground electronic states of NdO and NdS were determined as 15H (6s4fσ4fϕ4fδ) and 15H (4fϕ4fπ4fπ6s), with spectroscopic constants: bond length Re = 1.780 and 2.325 Å, and harmonic frequency ωe = 891 and 538 cm-1, respectively.

Probing Antioxidant-Related Properties for Phenolic Compounds.

In this work, properties related to antioxidant-potential mechanisms (such as the bond dissociation enthalpy, BDE, for the homolytic cleavage of the O-H bond and ionization energies, IEs) were determined for phenol, pyrocatechol, and gallic acid (GA). Both the protonated and deprotonated forms of GA were investigated. The Feller-Peterson-Dixon (FPD) composite method was employed with a variety of computational approaches, i.e., density functional theory, Möller-Plesset perturbation theory, and coupled-cluster-based methods, in combination with large correlation consistent basis sets with extrapolation to the complete basis set limit and consideration of core electron correlation effects. FPD results were compared to experimental and computational data available in the literature, presenting good agreement. For example, the FPD BDE (298 K) obtained for phenol, which was based on valence-correlated MP2/CBS calculations with contributions from correlating all electrons, was determined to be 87.56 kcal/mol, a value that is 0.42 kcal/mol lower than the result obtained in the most recent experiments, 87.98 ± 0.62. Calibration against coupled-cluster calculations was also carried out for phenol. We expect that the outcomes gathered here may help in establishing a general protocol for computational chemists that are interested in determining antioxidant-related properties for phenolic compounds with considerable accuracy as well as to motivate future IE measurements (particularly for GA) to be accomplished in the near future.

Electronic Structure Evolution in the Temperature Range of Metal–Insulator Transitions on Sn/Ge(111)

One‐third of monolayer of Sn adatoms on a Ge(111) substrate forms a 2D triangular lattice with one unpaired electron per site. The system presents a metal–insulator transition when decreasing the temperature and it is known to exhibit strong electron–phonon coupling at 120–150 K. Herein, a study of the electronic band structure for α‐Sn/Ge(111) between 150 and 5 K is reported. Both the experimental Fermi surfaces and the energy dispersions along high symmetry directions as a function of the temperature are presented. At 5 K it is observed a weakly or low‐dispersing spectral feature, exhibiting an extended gap in the reciprocal space. This feature is derived from the topmost occupied band, which is metallic at high temperature and which develops a kink associated with the strong electron–phonon coupling. The spectral evolution is partially explained with an increase of the electron–phonon coupling when decreasing the temperature. The increase of the electron–phonon coupling at low temperatures gives light into the new physics of this 2D system. The bandwidth is progressively reduced when reducing the temperature, enhancing the electronic correlation effects, and triggering the Mott transition.

Composition-driven Mott transition within SrTi 1−x V x O3

The last few decades has seen the rapid growth of interest in the bulk perovskite-type transition metal oxides SrVO3 and SrTiO3. The electronic configuration of these perovskites differs by one electron associated to the transition metal species which gives rise to the drastically different electronic properties. Therefore, it is natural to look into how the electronic structure transitions between these bulk structures by using doping. Measurements of the substitutional doped SrTi 1−x V x O3 shows an metal–insulator transition (MIT) as a function of doping. By using supercell density functional theory with dynamical mean field theory (DFT+DMFT), we show that the MIT is indeed the result of the combination of local electron correlation effects (Mott physics) within the t2g orbitals and the atomic site configuration of the transition metals which may indicate dependence on site disorder. SrTi 1−x V x O3 may be an ideal candidate for benchmarking cutting-edge Mott–Anderson models of real systems. We show that applying an effective external perturbation on SrTi 1−x V x O3 can switch the system between the insulating and metallic phase, meaning this is a bulk system with the potential use in Mott electronic devices.

Excited States by Coupling Piris Natural Orbital Functionals with the Extended Random-Phase Approximation.

In this work, we explore the use of Piris natural orbital functionals (PNOFs) to calculate excited-state energies by coupling their reconstructed second-order reduced density matrix with the extended random-phase approximation (ERPA). We have named the general method PNOF-ERPA, and specific approaches are referred to as PNOF-ERPA0, PNOF-ERPA1, and PNOF-ERPA2, according to the way the excitation operator is built. The implementation has been tested in the first excited states of H2, HeH+, LiH, Li2, and N2 showing good results compared to the configuration interaction (CI) method. As expected, an increase in accuracy is observed on going from ERPA0 to ERPA1 and ERPA2. We also studied the effect of electron correlation included by PNOF5, PNOF7, and the recently proposed global NOF (GNOF) on the predicted excited states. PNOF5 appears to be good and may even provide better results in very small systems, but including more electron correlation becomes important as the system size increases, where GNOF achieves better results. Overall, the extension of PNOF to excited states has been successful, making it a promising method for further applications.

A density-fitting implementation of the density-based basis-set correction method.

This work reports an efficient density-fitting implementation of the density-based basis-set correction (DBBSC) method in the MOLPRO software. This method consists in correcting the energy calculated by a wave-function method with a given basis set by an adapted basis-set correction density functional incorporating the short-range electron correlation effects missing in the basis set, resulting in an accelerated convergence to the complete-basis-set limit. Different basis-set correction density-functional approximations are explored and the complementary-auxiliary-basis-set single-excitation correction is added. The method is tested on a benchmark set of reaction energies at the second-order Møller-Plesset (MP2) level and a comparison with the explicitly correlated MP2-F12 method is provided. The results show that the DBBSC method greatly accelerates the basis convergence of MP2 reaction energies, without reaching the accuracy of the MP2-F12 method but with a lower computational cost.

Recent developments and applications of reference interaction site model self-consistent field with constrained spatial electron density (RISM-SCF-cSED): A hybrid model of quantum chemistry and integral equation theory of molecular liquids

The significance of solvent effects in electronic structure calculations has long been noted, and various methods have been developed to consider this effect. The reference interaction site model self-consistent field with constrained spatial electron density (RISM-SCF-cSED) is a hybrid model that combines the integral equation theory of molecular liquids with quantum chemistry. This method can consider the statistically convergent solvent distribution at a significantly lower cost than molecular dynamics simulations. Because the RISM theory explicitly considers the solvent structure, it performs well for systems where hydrogen bonds are formed between the solute and solvent molecules, which is a challenge for continuum solvent models. Taking advantage of being founded on the variational principle, theoretical developments have been made in calculating various properties and incorporating electron correlation effects. In this review, we organize the theoretical aspects of RISM-SCF-cSED and its distinctions from other hybrid methods involving integral equation theories. Furthermore, we carefully present its progress in terms of theoretical developments and recent applications.

Dynamic Correlations in Disordered Systems: Implications for High-Temperature Superconductivity

Liquids and gases are distinct in their extent of dynamic atomic correlations; in gases, atoms are almost uncorrelated, whereas they are strongly correlated in liquids. This distinction applies also to electronic systems. Fermi liquids are actually gas-like, whereas strongly correlated electrons are liquid-like. Doped Mott insulators share characteristics with supercooled liquids. Such distinctions have important implications for superconductivity. We discuss the nature of dynamic atomic correlations in liquids and a possible effect of strong electron correlations and Bose–Einstein condensation on the high-temperature superconductivity of the cuprates.

Computing electronic correlation energies using linear depth quantum circuits

Efficient computation of molecular energies is an exciting application of quantum computing for quantum chemistry, but current noisy intermediate-scale quantum (NISQ) devices can only execute shallow circuits, limiting existing variational quantum algorithms, which require deep entangling quantum circuit ansatzes to capture correlations, to small molecules. Here we demonstrate a variational NISQ-friendly algorithm that generates a set of Hartree–Fock ansatzes using multiple shallow circuits with depth linear in the number of qubits to estimate electronic correlation energies via perturbation theory up to the second order. We tested the algorithm on several small molecules, both with classical simulations including noise models and on cloud quantum processors, showing that it not only reproduces the equilibrium molecular energies but it also captures the perturbative electronic correlation effects at longer bond distances. The number of shallow circuits required for our algorithms scales O(N5) , with N being the system size, thus enabling the study of larger molecules compared to other approaches, where circuit depth or number of qubits required become prohibitive for NISQ devices.

Theoretical Prediction of Core-Level Binding Energies: Analysis of Unexpected Errors.

The analysis of the C(1s) and O(1s) core-level binding energies (CLBEs) of selected molecules computed by means of total energy Hartree-Fock (ΔSCF-HF) differences shows that in some cases, the calculated values for the C(1s) are larger than the experiment, which is unexpected. The origin of these unexpected errors of the Hartree-Fock ΔSCF BEs is shown to arise from static, nondynamical, electron correlation effects which are larger for the ion than for the neutral system. Once these static correlation effects are included by using complete active space self-consistent field (CASSCF) wave functions that include internal correlation terms, the resulting ΔSCF BEs are, as expected, smaller than measured values.

Chemical bonding effects in Sc compounds studied using X-ray absorption and X-ray photoelectron spectroscopies.

Advances on understanding the nature of the chemical bonding and electron correlation effects during the X-ray absorption process in ionic-covalent metal complexes has been achieved for most of the transition elements, except for scandium, due to the lack of a systematic series of spectroscopic reference spectra and the shortage of standard crystallographic data on scandium compounds. To close the gap, the chemical bonding effects in eight Sc compounds are studied using X-ray absorption spectroscopy (XAS) at Sc K and L2,3 absorption edges and X-ray photoelectron spectroscopy (XPS). Indeed, the fine structure of the XAS Sc K edge reflects the chemical sp3-like bond formed between scandium and the ligand while the L2,3 edge and the pre-edge features of the K-edge provide a direct insight into the crystal field parameters at the Sc site in the coordination compound. The XPS data provide the information on binding energies of the core electrons involved in the electron transitions caused by the absorption of high energy X-rays. XAS and XPS complement each other by accessing the information on Sc structure on bulk and the surface. Herein, comprehensive information on the electronic structure of well-known crystalline materials based on Sc is given with spectroscopic fingerprints X-ray data. This will help to predict the formation of chemical bonds in the unknown components via the systematic evaluation of the available spectroscopic fingerprints.

Influence of electronic correlation on the valley and topological properties of VSiGeP4 monolayer.

Valley is used as a new degree of freedom for information encoding and storage. In this work, the valley and topological properties of the VSiGeP4 monolayer were studied by adjusting the U value based on first-principles calculations. The VSiGeP4 monolayer remains in a ferromagnetic ground state regardless of the change in the U value. The magnetic anisotropy of the VSiGeP4 monolayer is initially in-plane, and then turns out-of-plane with the increase in the U value. Moreover, a topological phase transition is observed in the present VSiGeP4 monolayer with the increase in U value from 0 to 3 eV, i.e., the VSiGeP4 monolayer behaves as a bipolar magnetic semiconductor, a ferrovalley semiconductor, a half-valley metal characteristic, and a quantum anomalous Hall state. The mechanism of the topological phase transition behavior of the VSiGeP4 monolayer was analyzed. It was found that the variation in U values would change the strength of the electronic correlation effect, resulting in the valley and topological properties. In addition, carrier doping was studied to design a valleytronic device using this VSiGeP4 monolayer. By doping 0.05 electrons per f.u., the VSiGeP4 monolayer with a U value of 3 eV exhibits 100% spin polarization. This study indicates that the VSiGeP4 monolayer has potential applications in spintronic, valleytronic, and topological electronic nanodevices.

Doping effects of Kagome superconductor <i>A</i>V<sub>3</sub>Sb<sub>5</sub> (<i>A</i> = K, Rb, Cs)

Material with Kagome lattice provides an excellent platform for studying electronic correlation effects, topological states of matter, unconventional superconductivity, and geometric frustration. The recently discovered Kagome superconductors <i>A</i>V<sub>3</sub>Sb<sub>5</sub> (<i>A</i> = K, Rb, Cs) have attracted widespread attention in the field of condensed matter physics, and many efforts have been made to elucidate their novel physical properties, such as charge density wave, unconventional superconductivity, and band topology. Meanwhile, many groups have effectively tuned these novel properties through chemical doping, offering a good opportunity for further understanding the materials of this system. In this paper, we comprehensively review the latest research progress of the doping effect of this rapidly developed <i>A</i>V<sub>3</sub>Sb<sub>5</sub> system, with the objective of further promoting the in-depth research into Kagome superconductor. Specifically, we review the chemical doping in CsV<sub>3</sub>Sb<sub>5</sub> with elements such as Nb, Ta, Ti, and Sn, and the surface doping with elements Cs or O as well, and describe their influences on the novel quantum properties, especially superconductivity, charge density wave, and electronic band structure of the material. Furthermore, the intricate physical mechanism of doping manipulation is discussed, in order to provide a basic knowledge for further understanding and studying the rich quantum effects of the system, such as charge density waves, time reversal symmetry breaking, and superconductivity.

Two-dimensional ferromagnetism induced by Jahn-Teller distortion and orbital order

As the dimension of the system decreases, the quantum confinement effect and electronic correlation interaction inside the material will be correspondingly enhanced, often resulting in some novel physical properties. Recently, the freestanding perovskite oxide films down to the monolayer limit have been successfully prepared and can be transferred to any desired substrate, providing a great opportunity to explore the functional properties of two-dimensional perovskites. In perovskite materials, Jahn-Teller distortion and orbital order often cause a variety of correlated electronic behaviors. However, unlike van der Waals materials that retain their structural and chemical bonding characteristics when reduced to the monolayer limit, perovskite materials may undergo structural reconstruction when reduced to two dimensions. Therefore, whether Jahn-Teller distortion and related effects exist in the perovskite monolayer limit, and whether two-dimensional perovskite can exhibit some new properties different from its bulk phase, have become urgent issues to be solved. In this work, perovskite fluoride KCuF<sub>3</sub> and its monolayer have been comparatively studied by means of first-principles calculation, symmetry analysis, and Monte Carlo simulation methods, to reveal the change in lattice dynamics, structural, electronic, and magnetic properties caused by dimensionality reduction in perovskites. The results show that the cooperative Jahn-Teller distortion and the in-plane staggered orbital order occurring in the KCuF<sub>3</sub> bulk can be retained to the monolayer limit. However, unlike the bulk phase, the Jahn-Teller distortion mode appears as a soft mode of the prototype phase in the monolayer, and the insulating property of the monolayer does not rely on the emergence of the Jahn-Teller distortion, but is related to the enhancement of the electronic correlation effect. The staggered orbital order causes the nearest-neighbor exchange interaction to be ferromagnetic, resulting in the monolayer being a two-dimensional ferromagnetic insulator, different from the antiferromagnetic phase in the bulk. Monte Carlo simulations predict that the Curie temperature of the monolayer is about 5 K, which is much lower than the Néel temperature of the bulk phase, indicating that the disappearance of interlayer coupling leads to a significant reduction in the magnetic phase transition temperature. This work provides guidance and reference for the study of two-dimensional perovskite materials and the design of perovskite-based two-dimensional ferromagnets.

Iron Vacancy Tunable Superconductor-Insulator Transition in FeSe/SrTiO_{3} Monolayer.

The Fe_{4}Se_{5} with a sqrt[5]×sqrt[5] Fe vacancy order is suggested to be a Mott insulator and the parent state of bulk FeSe superconductor. The iron vacancy ordered state has been considered as a Mott insulator and the parent compound of bulk FeSe-based superconductors. However, for the superconducting FeSe/SrTiO_{3} monolayer (FeSe/STO) with an interface-enhanced high transition temperature (T_{c}), the electronic evolution from its Fe vacancy ordered parent phase to the superconducting state, has not been explored due to the challenge to realize an Fe vacancy order in the FeSe/STO monolayer, even though important to the understanding of superconductivity mechanism. In this study, we developed a new method to generate Fe vacancies within the FeSe/STO monolayer in a tunable fashion, with the assistance of atomic hydrogen. As a consequence, an insulating sqrt[5]×sqrt[5] Fe vacancy ordered monolayer is realized as the parent state. By using scanning tunneling microscopy and scanning tunneling spectroscopy, the spectral evolution from superconductivity to insulator is fully characterized. Surprisingly, a prominent spectral weight transfer occurs, thus implying a strong electron correlation effect. Moreover, the Fe vacancy induced insulating gap exhibits no Mott gap-like features. This work provides new insights in understanding the high-T_{c} superconductivity in FeSe/STO monolayer.

Theoretical study of electronic structure and ionization spectrum of γ-pyrone

The electronic structure and ionization spectrum of γ-pyrone (4 H -pyran-4-one) were studied using the third-order algebraic-diagrammatic construction method for a one-particle Green’s function [IP-ADC(3)] and a number of other high-level quantum chemical methods. The results of the calculations are used to interpret the recently obtained photoelectron spectra. A number of new assignments are proposed concerning the nature of the photoelectron maxima of γ-pyrone above 12 eV, where, according to our calculations, there is a significant violation of the single-electron ionization picture due to electron correlation effects. The results obtained significantly change the interpretation of the spectrum available in the literature.