Study Electron Correlation Research Articles

Modulation of Kondo Behavior in a Two-Dimensional Epitaxial Bilayer Bi(111)/Fe3GeTe2 Moiré Heterostructure.

Artificial two-dimensional (2D) moiré superlattices provide a platform for generating exotic quantum matter or phenomena. Here, an epitaxial heterostructure composed of bilayer Bi(111) and an Fe3GeTe2 substrate with a zero-twist angle is acquired by molecular beam epitaxy. Scanning tunneling microscopy and spectroscopy studies reveal the spatially tailored Kondo resonance and interfacial magnetism within this moiré superlattice. Combined with first-principles calculations, it is found that the modulation effect of the moiré superlattice originates from the interfacial orbital hybridization between Bi and Fe atoms. Our work provides a tunable platform for strong electron correlation studies to explore 2D artificial heavy Fermion systems and interface magnetism.

Bound-electron pairs within a repulsive Hubbard model in two-coupled linear chains

The study of electronic correlation in multiple layer materials provides an opportunity to understand the different pairing mechanism, their importance can be traced to the discovery of high Tc superconductors, superconductivity for a magic-angle in graphene lattices and others. In this work, we analyzed the two-interacting fermions in two-coupled periodic chains (ladder) within an attractive or repulsive potential, we obtain an analytical solution using the real-space mapping method. This real-space method is based on mapping the correlated many-body problem onto an equivalent tight-binding problem in a higher dimensional space. With this in mind, our ladder problem maps into a one-particle four dimensional lattice, which finally can be projected into an effective lattice of states in three dimensions. Two kind of solutions have been found, the antisymmetrical solution, which reduce the problem to two independent linear chains (one without impurities and the other with a central impurity) and the symmetrical solution corresponding to a ladder with an impurity. The latter solution is quite interesting since it allow us also to observe the new bound-electron pairs for E<0 in a repulsive potential (U>0).

Transition from Pauli paramagnetism to Curie-Weiss behavior in vanadium

We study electron correlations and their impact on magnetic properties of bcc vanadium by a combination of density functional and dynamical mean-field theory. The calculated uniform magnetic susceptibility {in bcc structure} is of Pauli type at low temperatures, while it obeys the Curie-Weiss law at higher temperatures. Thus, we qualitatively reproduce the experimental temperature dependence of magnetic susceptibility without introducing the martensitic phase transition. Our results for local spin-spin correlation function and local susceptibility reveal that the Curie-Weiss behavior appears due to partial formation of local magnetic moments, which originate from $t_{2g}$ states and occur due to local spin correlations caused by Hund's rule coupling. At the same time, the fermionic quasiparticles remain well-defined, while the formation of local moments is accompanied by a deviation from the Fermi-liquid behavior. In particular, the self-energy of the $t_{2g}$ states shows the non-analytic frequency dependence, which is a characteristic of the spin-freezing behavior, while the quasiparticle damping changes approximately linearly with temperature in the intermediate temperature range $200$--$700$~K. By analyzing the momentum dependence of static magnetic susceptibility, we find incommensurate magnetic correlations, which may provide a mechanism for unconventional superconductivity at low temperatures.

Investigating the Heaviest Halogen: Lessons Learned from Modeling the Electronic Structure of Astatine’s Small Molecules

We present a systematic study of electron-correlation and relativistic effects in diatomic molecular species of the heaviest halogen astatine (At) within relativistic single- and multireference coupled-cluster approaches and relativistic density functional theory. We establish revised reference ab initio data for the ground states of At2, HAt, AtAu, and AtO+ using a highly accurate relativistic effective core potential model and in-house basis sets developed for accurate modeling of molecules with large spin-orbit effects. Spin-dependent relativistic effects on chemical bonding in the ground state are comparable to the binding energy or even exceed it in At2. Electron-correlation effects near the equilibrium internuclear separation are mostly dynamical and can be adequately captured using single-reference CCSD(T). However, bond elongation in At2 and, especially, AtO+ results in rapid manifestation of its multireference character. While useful for evaluating the spin-orbit effects on the ground-state bonding and properties, the two-component density functional theory lacks predictive power, especially in combination with popular empirically adjusted exchange-correlation functionals. This drawback supports the necessity to develop new functionals for reliable quantum-chemical models of heavy-element compounds with strong relativistic effects.

Micromagnets dramatically enhance effects of viscous hydrodynamic flow in a two-dimensional electron fluid

The hydrodynamic behavior of electron fluids in a certain range of temperatures and densities is well established in graphene and in two-dimensional semiconductor heterostructures. The hydrodynamic regime is intrinsically based on electron-electron interactions, and therefore it provides a unique opportunity to study electron correlations. Unfortunately, in simple longitudinal resistance measurements, the relative contribution of hydrodynamic effects to transport is rather small, especially at higher temperatures. Viscous hydrodynamic effects are masked by impurities, interaction with phonons, uncontrolled boundaries, and ballistic effects. This essentially limits the accuracy of measurements of electron viscosity. Fundamentally, what causes viscous friction in the electron fluid is the property of the flow called vorticity. In this paper, we propose to use micromagnets to increase the vorticity by orders of magnitude. Experimental realization of this proposal will bring electron hydrodynamics to a qualitatively new precision level, as well as opening a new way to characterize and externally control the electron fluid.

Monitoring Argon L-Shell Auger Decay Using 250-eV Attosecond X-ray Pulses.

Electron correlation describes the interaction between electrons in a multi-electron system. It plays an important role in determining the speed of relaxation of atoms and molecules excited by XUV/X-ray pulses, such as the argon decay rate. Most research on electron correlation has centered on the role of correlation in stationary states. A time-resolved experimental study of electron correlation is a grand challenge due to the required temporal resolution and photon energy. In this research, we investigated Auger decay in argon using 200-attosecond X-ray pulses reaching the carbon K-edge. At such a high photon energy, ionization occurs not only from the outer most levels (3s and 3p), but also from the 2p core shells. We have measured a lifetime of 4.9 fs of L-shell vacancies of argon in pump–probe experiments with a home-built high-resolution time-of-flight spectrometer.

Magnetic-Field Effect as a Tool to Investigate Electron Correlation in Strong-Field Ionization

The influence of the magnetic component of the driving electromagnetic field is often neglected when investigating light-matter interaction. We show that the magnetic component of the light field plays an important role in nonsequential double ionization, which serves as a powerful tool to investigate electron correlation. We investigate the magnetic-field effects in double ionization of xenon atoms driven by near-infrared ultrashort femtosecond laser pulses and find that the mean forward shift of the electron momentum distribution in light-propagation direction agrees well with the classical prediction, where no under-barrier or recollisional nondipole enhancement is observed. By extending classical trajectory MonteCarlo simulations beyond the dipole approximation, we reveal that double ionization proceeds via recollision-induced doubly excited states, followed by subsequent sequential over-barrier field ionization of the two electrons. In agreement with this model, the binding energies do not lead to an additional nondipole forward shift of the electrons. Our findings provide a new method to study electron correlation by exploiting the effect of the magnetic component of the electromagnetic field.

Unconventional superconductivity near a flat band in organic and organometallic materials

We study electron correlation driven superconductivity on a decorated honeycomb lattice (DHL), which has a low-energy flat band. On doping, we find singlet superconductivity with extended-s, extended-d and f-wave symmetry mediated by magnetic exchange. f-wave singlet pairing is enabled by the lattice decoration. The critical temperature is predicted to be significantly higher than on similar lattices lacking flat bands. We discuss how high-temperature superconductivity could be realized in the DHL materials such as Rb3TT. 2 H2O and Mo3S7(dmit)3.

An investigation of photo-double ionization in benzene

SynopsisA photo-double ionization (PDI) coincidence technique has been used to study electron correlation as a function of photon impact energy on Benzene (C6H6). The simultaneous emission of two photoelectrons from the benzene π orbital has been measured using two sets of hemispherical electron energy analysers. Angle resolved single and coincidence photoelectron spectra are reported, providing new data on the PDI mechanism.

Atomic Form Factor Calculations of S-states of Helium

Variational calculations of the helium atom states are performed using highly compact 26-parameter correlated Hylleraas-type wave functions. These correlated wave functions used here yield an accurate expectation energy values for helium ground and two first excited states. A correlated wave function consists of a generalized exponential expansion in order to take care of the correlation effects due to N-corps interactions. The parameters introduced in our model are determined numerically by minimization of the total atomic energy of each electronic configuration. We have calculated all integrals analytically before dealing with numerical evaluation. The 1S2 11S and 1S2S 21, 3S states energies, charge distributions and scattering atomic form factors are reported. The present work shows high degree of accuracy even with relative number terms in the trial Hylleraas wave functions definition. The results presented here, indicate that the highly compact twenty-six variational parameters model will have the quantitative and qualitative applicability for the study of electronic correlation. The correlated wave functions are used to calculate the atomic form factor for the diffusion of electrons by the helium atom. The atomic form factor is evaluated as the Fourier transform of the electron density distribution of an atom or ion, which is calculated from theoretical correlated wave functions for free atoms. Finally, suggestions are made as to the way the atomic form factor of the helium atom may be approximated by a sum of Gaussians for efficiency use.

On the geometric dependence of the molecular dipole polarizability in water: A benchmark study of higher-order electron correlation, basis set incompleteness error, core electron effects, and zero-point vibrational contributions.

In this work, we investigate how geometric changes influence the static dipole polarizability (α) of a water molecule by explicitly computing the corresponding dipole polarizability surface (DPS) across 3125 total (1625 symmetry-unique) geometries using linear response coupled cluster theory including single, double, and triple excitations (LR-CCSDT) and the doubly augmented triple-ζ basis set (d-aug-cc-pVTZ). Analytical formulae based on power series expansions of this ab initio surface are generated using linear least-squares analysis and provide highly accurate estimates of this quantity as a function of molecular geometry (i.e., bond and angle variations) in a computationally tractable manner. An additional database, which consists of 25 representative molecular geometries and incorporates a more thorough treatment of both basis sets and core electron effects, is provided as a current benchmark for this quantity and the corresponding leading-order C 6 dispersion coefficient. This database has been utilized to assess the importance of these effects as well as the relative accuracy that can be obtained using several quantum chemical methods and a library of density functional approximations. In addition to high-level electron correlation methods (like CCSD) and our analytical least-squares formulae, we find that the SCAN0, PBE0, MN15, and B97-2 hybrid functionals yield the most accurate descriptions of the molecular polarizability tensor in H2O. Using first-order perturbation theory, we compute the zero-point vibrational correction to α at the CCSDT/d-aug-cc-pVTZ level and find that this correction contributes approximately 3% to the isotropic (α iso) and nearly 50% to the anisotropic (α aniso) polarizability values. In doing so, we find that α iso = 9.8307 bohr3, which is in excellent agreement with the experimental value of 9.83 ± 0.02 bohr3 provided by Russell and Spackman. The DPS reported herein provides a benchmark-quality quantum mechanical estimate of this fundamental quantity of interest and should find extensive use in the development (and assessment) of next-generation force fields and machine-learning based approaches for modeling water in complex condensed-phase environments.

Electronic and Vibrational Hyperpolarizabilities of Lithium Substituted (Aza)benzenes and (Aza)naphthalenes

In this article we report results for the electronic and vibrational hyperpolarizabilities of ten molecules: Li@benzene, Li@pyridine, Li@pyrimidine, and Li@pyrazine; Li@naphthalene, Li@quinoline, Li@isoquinoline, Li@cinnolin, Li@quinazoline, and Li@quinoxaline. An electron correlation study shows that second-order many-body perturbation theory and density functional theory with CAM-B3LYP and M05-2X functionals give results for the electronic hyperpolarizabilities in good agreement with coupled cluster with single and doubles reference values. Static and dynamic vibrational corrections were computed through the perturbation theoretical method of Bishop and Kirtman and using a variational approach. In general, we obtained notable discrepancies between the results obtained by the two methods for the pure vibrational corrections because of the deficiency of the perturbation method to properly treat low-frequency normal modes present in the investigated systems. However, both methods give results similar to the zero-point vibrational average corrections.

Multiconfiguration time-dependent Hartree-Fock treatment of electron correlation in strong-field ionization of H2 molecules

Electron correlation plays an important role in the multielectron interactions of many physical and chemical processes.The investigation of correlation effects in the non-perturbative electronic dynamics (e.g.non-sequential double ionization) when atoms and molecules are subjected to strong laser fields requires non-perturbative theoretical treatments. The direct numerical integration of the time-dependent Schrödinger equation successfully explains many experimental results,but it is computationally prohibitive for systems with more than two electrons.There is clearly a need for a theory which can treat correlation dynamics self-consistently in strong time-dependent electric fields.In this paper we develop a three-dimensional multiconfiguration time-dependent Hartree-Fock method,which can be applied to the non-perturbative electronic dynamics for diatomic molecules,and it can also investigate the effect of electron correlation in strong-field ionization of H2 molecules.This method adopts the prolate spheroidal coordinates (which can treat the two-center Coulomb potential accurately) and the finite-element method together with discrete-variable representation (which lowers the calculation burden from two-electron integrations).For the temporal propagation,we use the efficient short iterative Lanczos algorithm for the equation which governs the configuration expansion coefficients,while an eight-order Runge-Kutta (RK) method and an Bulirsch-Stoer (BS) extrapolation method,both with adaptive precision controls,are implemented to solve the nonlinear orbital equation.While both methods yield correct results,the BS method displays a better stability in the realtime propagation,while the RK method demands less computation.The alignment-dependent ionization probabilities of H2 molecules in intense extreme ultraviolet pulses are calculated.Comparisons between multi-configuration and single-configuration results show that electron correlation has little effect on the single ionization process,but it plays an important role in double ionization,leading to the decrease in the ionization probability.The double ionization probability from the single-configuration space 1σ is about three times larger that from 4σ1π.The ionization probability increases monotonically when the alignment angle increases from 0° to 90°, yielding a ratio of 2.6(1.5) between 90° and 0° for the double (single) ionization process.This method presents the basis for the future study of electron correlation in strong-field processes.

Electron-correlation study of Y iii-Tc vii ions using a relativistic coupled-cluster theory

Spectroscopic properties, useful for plasma diagnostics and astrophysics, of a few rubidium-like ions are studied here. We choose one of the simplest, but correlationally challenging series where d- and f-orbitals are present in the core and/or valence shells with as the ground state. We study different correlation characteristics of this series and make precise calculations of electronic structure and rates of electromagnetic transitions. Our calculated lifetimes and transition rates are compared with other available experimental and theoretical values. Radiative rates of vacuum ultraviolet electromagnetic transitions of the long lived Tc6+ ion, useful in several areas of physics and chemistry, are estimated. To the best of our knowledge, there is no literature for most of these transitions.

The tight-binding formulation of the Kronig-Penney model

Electronic band structure calculations are frequently parametrized in tight-binding form; the latter representation is then often used to study electron correlations. In this paper we provide a derivation of the tight-binding model that emerges from the exact solution of a particle bound in a periodic one-dimensional array of square well potentials. We derive the dispersion for such a model, and show that an effective next-nearest-neighbour hopping parameter is required for an accurate description. An electron-hole asymmetry is prevalent except in the extreme tight-binding limit, and emerges through a “next-nearest-neighbour” hopping term in the dispersion. We argue that this does not necessarily imply next-nearest-neighbour tunneling; this assertion is demonstrated by deriving the transition amplitudes for a two-state effective model that describes a double-well potential, which is a simplified precursor to the problem of a periodic array of potential wells. A next-nearest-neighbour tunneling parameter is required for an accurate description even though there are no such neighbours.

Static second hyperpolarizability of diffuse electron compound M2X (M = Li, na; X = H, F): Ab-initio study of basis set effect and electron correlation

Present investigation reveals that diffuse electron compounds M2X predict large (106a.u.) γav value. The basis set dependence of γav showed that the quality of basis function rather than its size is more important. Sadlej’s Pol basis set which is nearly four times less in size than aug-cc-pVQZ can give reliable estimate of γav. MP2 method in conjunction with large basis sets can give comparable results of γav that could be obtained from CCSD or CCSD(T). Higher order energy correction to MP2 leads to oscillatory behavior but inclusion of triple excitations to CCSD improves the magnitude of γav.

Observation of the frozen charge of a Kondo resonance.

The ability to control electronic states at the nanoscale has contributed to our modern understanding of condensed matter. In particular, quantum dot circuits represent model systems for the study of strong electronic correlations, epitomized by the Kondo effect. We use circuit quantum electrodynamics architectures to study the internal degrees of freedom of this many-body phenomenon. Specifically, we couple a quantum dot to a high-quality-factor microwave cavity to measure with exceptional sensitivity the dot's electronic compressibility, that is, its ability to accommodate charges. Because electronic compressibility corresponds solely to the charge response of the electronic system, it is not equivalent to the conductance, which generally involves other degrees of freedom such as spin. Here, by performing dual conductance and compressibility measurements in the Kondo regime, we uncover directly the charge dynamics of this peculiar mechanism of electron transfer. The Kondo resonance, visible in transport measurements, is found to be 'transparent' to microwave photons trapped in the high-quality cavity, thereby revealing that (in such a many-body resonance) finite conduction is achieved from a charge frozen by Coulomb interaction. This freezing of charge dynamics is in contrast to the physics of a free electron gas. We anticipate that the tools of cavity quantum electrodynamics could be used in other types of mesoscopic circuits with many-body correlations, providing a model system in which to perform quantum simulation of fermion-boson problems.

Correlated electron dynamics in strong-field double ionization

In intense laser-atom/molecule interaction, there are many new phenomena involving multielectron effects. As one of the most important strong-field process, strong-field double ionization of atoms and molecules, especially the strong-field nonsequential double ionization (NSDI), exhibits highly correlated behaviors, providing a clean way to study electron correlation in nature. We review the microscopic electron dynamics of NSDI revealed by recent experimental studies based on the COLTRIMS and the related theory contributions. We summarized the laser intensity-dependent microscopic electron dynamics of NSDI. At low laser intensities, NSDI is dominated by the recollision-excitation with subsequent field ionization, and the time delay between the final ionizations of the two electrons could results in the experimental observed back-to-back emission of the electron pairs. As the laser intensity increases, recollision induced direct ionization dominates NSDI and two electrons ionized almost simultaneously after recollision. In this process the final-state ion-electron attraction and electron repulsion significantly affect the details of the electron correlation pattern. As the laser intensity further increases, the role of final-state ion-electron and electron-electron interactions becomes less important, and the asymmetric energy sharing at recollision is prevalent which accounts for the strange V-like shape in the correlated electron momentum spectra at very high laser intensity. We also introduced the control of the correlated electron dynamics. It has been theoretically predicted that the electron pairs can be controlled to exhibit correlated or anticorrelated behavior with the two-color field, which has been proved by experiment. We also review the progress on strong-field sequential double ionization (SDI). Recent experiments have observed many phenomena which conflicted with the predictions of the previous theoretical models of SDI. Here we introduced a recent developed model of strong-field SDI, which successfully explained the new experimental results and predicted many interesting results.

Exploring heavy fermions from macroscopic to microscopic length scales

Strongly correlated systems present fundamental challenges, especially in materials in which electronic correlations cause a strong increase of the effective mass of the charge carriers. Heavy fermion metals — intermetallic compounds of rare earth metals (such as Ce, Sm and Yb) and actinides (such as U, Np and Pu) — are prototype systems for complex and collective quantum states; they exhibit both a lattice Kondo effect and antiferromagnetic correlations. These materials show unexpected phenomena; for example, they display unconventional superconductivity (beyond Bardeen–Cooper–Schrieffer (BCS) theory) and unconventional quantum criticality (beyond the Landau framework). In this Review, we focus on systems in which Landau's Fermi-liquid theory does not apply. Heavy fermion metals and semiconductors are well suited for the study of strong electronic correlations, because the relevant energy scales (for charge carriers, magnetic excitations and lattice dynamics) are well separated from each other, allowing the exploration of concomitant physical phenomena almost independently. Thus, the study of these materials also provides valuable insight for the understanding — and tailoring — of other correlated systems. Heavy fermion systems are ideally suited to study strong electronic correlations. These fascinating materials are characterized by a clear separation of the relevant energy scales and may exhibit quantum critical points, non-Fermi-liquid behaviour and unconventional superconductivity coexisting or competing with magnetism.

Correlated electronic states of SrVO3 revealed by angle-resolved photoemission spectroscopy

In this article, we review recent progress in angle-resolved photoemission (ARPES) studies of the Mott-Hubbard-type correlated electron systems SrVO3. It has the d1 electron configuration and is an ideal model compound to study electron correlation effects in normal metal. ARPES studies of bulk single-crystal SrVO3 and CaVO3 have revealed the difference in the mass renormalization of electrons between them. In-situ ARPES studies of thin films fabricated by the pulsed laser deposition method have clarified not only quasi-particle dispersions, which show a kink like high-Tc cuprates, but also finite dispersions in the incoherent part. Self-energy in a wide energy range has been deduced from the ARPES spectral weight using Kramers–Kronig transformation. The obtained self-energy has several structures which yield the incoherent feature and a pseudogap-like dip similar to the high-Tc cuprates. Quantum-well states in ultrathin films of SrVO3 have revealed sub-bands with correlated electrons. These findings of electron correlation effects outlined in the present article would provide a starting point not only for fundamental condensed-matter physics but also for the development of new devices with correlated electrons.