Importance Of Many-body Effects Research Articles

Designable exciton mixing through layer alignment in WS2-graphene heterostructures

Optical properties of heterostructures composed of layered 2D materials, such as transition metal dichalcogenides (TMDs) and graphene, are broadly explored. Of particular interest are light-induced energy transfer mechanisms in these materials and their structural roots. Here, we use state-of-the-art first-principles calculations to study the excitonic composition and the absorption properties of WS2–graphene heterostructures as a function of interlayer alignment and the local strain resulting from it. We find that Brillouin zone mismatch and the associated energy level alignment between the graphene Dirac cone and the TMD bands dictate an interplay between interlayer and intralayer excitons, mixing together in the many-body representation upon the strain-induced symmetry breaking in the interacting layers. Examining the representative cases of the 0° and 30° interlayer twist angles, we find that this exciton mixing strongly varies as a function of the relative alignment. We quantify the effect of these structural modifications on exciton charge separation between the layers and the associated graphene-induced homogeneous broadening of the absorption resonances. Our findings provide guidelines for controllable optical excitations upon interface design and shed light on the importance of many-body effects in the understanding of optical phenomena in complex heterostructures.

Electronic structure of CeCu4In from band structure calculations and X-ray photoelectron spectroscopy

We present a combined new experimental and theoretical study of the electronic structure for the heavy fermion CeCu4In based on X-ray photoelectron spectroscopy (XPS) data and ab-initio band structure calculations. The compound crystallizes in the orthorhombic CeCu4.38In1.62 type of structure (space group Pnnm). Below the Fermi energy the total density of states contains mainly 3d–states of Cu atoms that hybridized with the Ce 4f electronic states. The Ce core-level XPS spectra point to a stable trivalent configuration of Ce atoms in CeCu4In, consistently with the magnetic susceptibility data. For more detailed information about electronic states the fully relativistic band structure was calculated within the density functional theory (DFT) for the first time. Based on these calculations we present calculated photoemission spectra, which very well reproduce the experimental ones. The Fermi level is located at a deep decrease in the density of electronic states and reaches a value of 3.69 states/(eV f.u.). This value is much smaller than the one obtained experimentally, which indicates the importance of many-body effects, which are not properly taken into account in ab-initio calculations. The valence band is formed mainly by Cu(3d) electrons with a small contribution of Ce(4f) electrons in the immediate vicinity of the Fermi level.

Importance of the many-body effects on the structural properties of the novel iron oxide Fe2O.

The importance of many-body effects on the electronic and magnetic properties and stability of different structural phases was studied in novel iron oxide Fe2O. It was found that while Hubbard repulsion hardly affects the electronic spectrum of this material (m*/m ≈ 1.2), it strongly changes its phase diagram, shifting critical pressures of structural transitions to much lower values. Moreover, the P3̄m1 structure previously obtained in the density functional theory (DFT) becomes energetically unstable if many-body effects are taken into consideration. It is shown that these changes are due to magnetic moment fluctuations in the DFT+DMFT (method which combines density functional theory and dynamical mean-field theory) approach, which strongly modify the phase diagram of Fe2O.

Origin of the complex main and satellite features in Fe 2p XPS of Fe2O3.

Although the origin and assignment of the complex XPS features of the cations in ionic compounds has been the subject of extensive theoretical work, agreement with experimental observations remains insufficient for unambiguous interpretation. This paper presents a rigorous ab initio treatment of the main and satellite features in the Fe 2p XPS of Fe2O3. This has been possible using a unique methodology for the selection of orbitals that are used to form the ionic wavefunctions. This orbital selection makes it possible to treat both the angular momentum coupling of the open shell core and valence electrons as well the shake excitations from the closed shell orbitals associated with the O ligands into the valence open shell orbitals associated with the Fe 3d shell. This allows the character of the ionic states in terms of the occupations of the open shell core and valence orbitals and of the contributions of 2p1/2 and 2p3/2 ionization to the XPS intensities to be determined. Our analysis gives strong evidence that many body effects are essential for a correct description of the ionic states and, in general the states cannot be described by a single configuration over the open shell orbitals. An important consequence is that the Fe 2p XPS intensity in most of the features arises from small contributions from the ionization to many, tens to hundreds, of often unresolved ionic states. While the usual understanding of the lower binding energy main and satellite features as being dominantly from 2p3/2 ionization is confirmed, this is not the case for the higher binding energy features where 2p1/2 and 2p3/2 ionization and shake excitations in the valence space mix strongly. Furthermore, we have been able to show that a very large fraction, 88%, of the total Fe 2p XPS intensity is contained in a relatively small binding energy range of ∼35 eV. This is relevant if one wants to extract the stoichiometry of Fe2O3 from Fe 2p/O 1s intensity ratios. Similar considerations about the importance of many-body effects are likely to be relevant for other ionic compounds as well.

Relativistic many-body theory of the electric dipole moment of Xe129 and its implications for probing new physics beyond the standard model

We report the results of our theoretical studies of the time-reversal and parity violating electric dipole moment (EDM) of $^{129}$Xe arising from the nuclear Schiff moment (NSM) and the electron-nucleus tensor-pseudotensor (T-PT) interaction based on the self-consistent and the normal relativistic coupled-cluster methods. The important many-body effects are highlighted and their contributions are explicitly presented. The uncertainties in the calculations of the correlation and relativistic effects are determined by estimating the contributions of the triples excitations, and the Breit interaction respectively, which together amount to about 0.7% for the NSM and 0.2% for the T-PT interactions. The results of our present work in combination with improved experimental limits for $^{129}$Xe EDM in the future would tighten the constraints on the hadronic CP violating quantities, and this could provide important insights into new physics beyond the Standard Model of elementary particles.

Assessing Many-Body Effects of Water Self-Ions. II: H3O+(H2O)n Clusters

The importance of many-body effects in the hydration of the hydronium ion (H3O+) is investigated through a systematic analysis of the many-body expansion of the interaction energy carried out at the coupled-cluster level of theory for the low-lying isomers of H3O+(H2O)n clusters with n = 1-5. This is accomplished by partitioning individual fragments extracted from the whole clusters into "groups" that are classified by both the number of H3O+ and water molecules and the hydrogen-bonding connectivity within a given fragment. Effects due to the presence of the Zundel ion, (H5O2)+, are analyzed by further partitioning fragment groups by the "context" of their parent clusters. With the aid of the absolutely localized molecular orbital energy decomposition analysis (ALMO EDA), this structure-based partitioning is found to largely correlate with the character of different many-body interactions, such as cooperative and anticooperative hydrogen bonding, within each fragment. This analysis emphasizes the importance of a many-body representation of inductive electrostatics and charge transfer in modeling the hydration of an excess proton in water. The comparison between the reference coupled-cluster many-body interaction terms with the corresponding values obtained with various exchange-correlation functionals demonstrates that many of these functionals yield an unbalanced treatment of the H3O+(H2O)n configuration space.

On the Phase Diagrams of 4He Adsorbed on Graphene and Graphite from Quantum Simulation Methods

The ground-state phase diagrams of 4 He adsorbed on graphene and graphite are calculated using quantum simulation methods. In this work, a systematic investigation of the approximations used in such simulations is carried out. Particular focus is placed on the helium–helium (He–He) and helium–carbon (He–C) interactions, as well as their modern approximations. On careful consideration of other approximations and convergence, the simulations are otherwise (numerically) exact. The He–He interaction as approximated by a sum of pairwise potentials is quantitatively assessed. A similar analysis is made for the He–C interaction, but more thoroughly and with a focus on surface corrugation. The importance of many-body effects is discussed. Altogether, the results provide “reference data” for the considered systems. Using comparisons with experiments and first-principle calculations, conclusions are drawn regarding the quantitative accuracy of these modern approximations to these interactions.

Assessing Many-Body Effects of Water Self-Ions. I: OH-(H2O) n Clusters.

The importance of many-body effects in the hydration of the hydroxide ion (OH-) is investigated through a systematic analysis of the many-body expansion of the interaction energy carried out at the CCSD(T) level of theory, extrapolated to the complete basis set limit, for the low-lying isomers of OH-(H2O) n clusters, with n = 1-5. This is accomplished by partitioning individual fragments extracted from the whole clusters into "groups" that are classified by both the number of OH- and water molecules and the hydrogen bonding connectivity within each fragment. With the aid of the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA) method, this structure-based partitioning is found to largely correlate with the character of different many-body interactions, such as cooperative and anticooperative hydrogen bonding, within each fragment. This analysis emphasizes the importance of a many-body representation of inductive electrostatics and charge transfer in modeling OH- hydration. Furthermore, the rapid convergence of the many-body expansion of the interaction energy also suggests a rigorous path for the development of analytical potential energy functions capable of describing individual OH--water many-body terms, with chemical accuracy. Finally, a comparison between the reference CCSD(T) many-body interaction terms with the corresponding values obtained with various exchange-correlation functionals demonstrates that range-separated, dispersion-corrected, hybrid functionals exhibit the highest accuracy, while GGA functionals, with or without dispersion corrections, are inadequate to describe OH--water interactions.

Probing electronic structure of stoichiometric and defectiveSnO2

The electronic structure of stoichiometric tin dioxide ($\mathrm{Sn}{\mathrm{O}}_{2}$) is studied by probing its unoccupied states using the fine structure in the electron energy-loss spectra (EELS) at the oxygen-$K$ (O-$K$) edge. The spectral measurements were performed both at room and at high temperatures (773 K) and compared to ab initio calculations carried out using the real-space multiple-scattering and linearized augmented-plane-wave methods. Important many-body effects are included via quasiparticle corrections calculated within the many-pole $GW$ self-energy approximation. An additional energy-dependent damping is calculated to account for vibrational effects. Results from this paper demonstrated that quantitative agreement between theoretical and experimental spectra can be obtained when nonspherical potentials and quasiparticle self-energy effects are considered and vibrational broadening is included. Modifications of the electronic structure by single oxygen vacancies, both in the bulk and at the (110) surface, also are predicted. Our predictions support the use of O-$K$ EELS as a probe of the defect structures in $\mathrm{Sn}{\mathrm{O}}_{2}$ surfaces and nanoparticles.

Analytical solutions for semiconductor luminescence including Coulomb correlations with applications to dilute bismides

In this paper we introduce analytical solutions of interband polarization, which is the self-energy of the Dyson equation for the photon Green’s functions, and apply them to studying photoluminescence of Coulomb-correlated semiconductor materials. The accuracy of the easily programmable solutions is proven by consistently demonstrating the low-temperature s-shape of the luminescence peak of dilute bismide semiconductors. The different roles of homogeneous versus inhomogeneous broadening at low and high temperatures are described, as well as the importance of many body effects, which are in very good agreement with experiments.

Ultrafast photoelectron migration in dye-sensitized solar cells: Influence of the binding mode and many-body interactions.

In the present contribution, the ultrafast photoinduced electron migration dynamics at the interface between an alizarin dye and an anatase TiO2 thin film is investigated from first principles. Comparison between a time-dependent many-electron configuration interaction ansatz and a single active electron approach sheds light on the importance of many-body effects, stemming from uniquely defined initial conditions prior to photoexcitation. Particular emphasis is put on understanding the influence of the binding mode on the migration process. The dynamics is analyzed on the basis of a recently introduced toolset in the form of electron yields, electronic fluxes, and flux densities, to reveal microscopic details of the electron migration mechanism. From the many-body perspective, insight into the nature of electron-electron and hole-hole interactions during the charge transfer process is obtained. The present results reveal that the single active electron approach yields quantitatively and phenomenologically similar results as the many-electron ansatz. Furthermore, the charge migration processes in the dye-TiO2 model clusters with different binding modes exhibit similar mechanistic pathways but on largely different time scales.

Many-body effects on the resistivity of a multi-orbital system beyond Landau's Fermi-liquid theory

I review many-body effects on the resistivity of a multi-orbital system beyond Landau's Fermi-liquid (FL) theory. Landau's FL theory succeeds in describing electronic properties of some correlated electron systems at low temperatures. However, the behaviors deviating from the temperature dependence in the FL, non-FL-like behaviors, emerge near a magnetic quantum-critical point (QCP). These indicate the importance of many-body effects beyond Landau's FL theory. Those effects in multi-orbital systems have been little understood, although their understanding is important to deduce ubiquitous properties of correlated electron systems and characteristic properties of multi-orbital systems. To improve this situation, I formulate the resistivity of a multi-orbital Hubbard model using the extended Éliashberg theory and adopt this method to the inplane resistivity of quasi-two-dimensional paramagnetic ruthenates in combination with the fluctuation-exchange approximation including the current vertex corrections arising from the self-energy and Maki–Thompson term. The results away from and near the antiferromagnetic QCP reproduce the temperature dependence observed in Sr 2 RuO 4 and Sr 2 Ru 0.075 Ti 0.025 O 4, respectively. I highlight the importance of not only the momentum and the temperature dependence of the damping of a quasiparticle but also its orbital dependence in discussing the resistivity of correlated electron systems.

Collecting high-order interactions in an effective pairwise intermolecular potential using the hydrated ion concept: the hydration of Cf³⁺.

This work proposes a new methodology to build interaction potentials between a highly charged metal cation and water molecules. These potentials, which can be used in classical computer simulations, have been fitted to reproduce quantum mechanical interaction energies (MP2 and BP86) for a wide range of [M(H2O)n](m+)(H2O)ℓ clusters (n going from 6 to 10 and ℓ from 0 to 18). A flexible and polarizable water shell model (Mobile Charge Density of Harmonic Oscillator) has been coupled to the cation-water potential. The simultaneous consideration of poly-hydrated clusters and the polarizability of the interacting particles allows the inclusion of the most important many-body effects in the new polarizable potential. Applications have been centered on the californium, Cf(III) the heaviest actinoid experimentally studied in solution. Two different strategies to select a set of about 2000 structures which are used for the potential building were checked. Monte Carlo simulations of Cf(III)+500 H2O for three of the intermolecular potentials predict an aquaion structure with coordination number close to 8 and average R(Cf-O) in the range 2.43-2.48 Å, whereas the fourth one is closer to 9 with R(Cf-O) = 2.54 Å. Simulated EXAFS spectra derived from the structural Monte Carlo distribution compares fairly well with the available experimental spectrum for the simulations bearing 8 water molecules. An angular distribution similar to that of a square antiprism is found for the octa-coordination.

Recent progress in EXAFS/NEXAFS spectroscopy

We briefly review the basic theory and recent applications in the X-ray absorption fine structure (XAFS) spectroscopy. First we discuss a dressed one-electron XAFS formula starting from many-body scattering theory, where important many-body effects, intrinsic and extrinsic losses, and optical potential are naturally introduced. Next multiple scattering renormalization, and spherical wave effects are discussed. Phonon effects such as Debye–Waller factors are also discussed. Some interesting XAFS applications, in particular, ultrafast XAFS and XAFS applications to nano-particles are discussed in some detail.

Importance of Many-Body Effects in the Kernel of Hemoglobin for Ligand Binding

We propose a mechanism for binding of diatomic ligands to heme based on a dynamical orbital selection process. This scenario may be described as bonding determined by local valence fluctuations. We support this model using linear-scaling first-principles calculations, in combination with dynamical mean-field theory, applied to heme, the kernel of the hemoglobin metalloprotein central to human respiration. We find that variations in Hund's exchange coupling induce a reduction of the iron 3d density, with a concomitant increase of valence fluctuations. We discuss the comparison between our computed optical absorption spectra and experimental data, our picture accounting for the observation of optical transitions in the infrared regime, and how the Hund's coupling reduces, by a factor of 5, the strong imbalance in the binding energies of heme with CO and O(2) ligands.

Simulating the miscibility of nanoparticles and polymer melts

While the miscibility and spatial dispersion of nanoparticles (NPs) in a polymer melt critically affects the properties of the resulting nanocomposite, little simulation work exists on understanding this critical issue. We use isothermal–isobaric ensemble simulations and show that larger NPs disperse more easily than small NPs, implying the relative dominance of NP–polymer attractions over depletion-induced inter-NP attractions. Similarly, polymer chain length only plays a secondary role, probably because the entropic, depletion-induced inter-NP attractions only occur over length scales comparable to the correlation length in the melt, namely the segment size, σ. Importantly, no NP self-assembly is observed, and the only transition that occurs for polymer systems with large enough NPs (σNP ≥ 6σ) is of a purely, first-order solid–fluid type. This result follows from the fact that the range of effective attractions between the NPs, δ = σ/σNP, is short enough to preclude a vapor–liquid transition. This finding is given more weight since an equivalent sticky sphere model can reproduce the essence of our simulations. The observed behavior is captured by an effective two-body, polymer-mediated, inter-NP interaction potential, a surprising result in light of conventional wisdom in this field which implies the importance of many body effects.

Coherent measurements of high-order electronic correlations in quantum wells

Strong, long-range Coulomb interactions can lead to correlated motions of multiple charged particles, which can induce important many-body effects in semiconductors. The exciton states formed from correlated electron-hole pairs have been studied extensively, but basic properties of multiple-exciton correlations-such as coherence times, population lifetimes, binding energies and the number of particles that can be correlated-are largely unknown because they are not spectroscopically accessible from the ground state. Here we present direct observations of high-order coherences in gallium arsenide quantum wells, achieved using two-dimensional multiple-quantum spectroscopy methods in which up to seven successive light fields were used. The measurements were made possible by the combination of a reconfigurable spatial beam-shaper that formed multiple beams in specified geometries and a spatiotemporal pulse-shaper that controlled the relative optical phases and temporal delays among pulses in all the beams. The results reveal triexciton coherences (correlations of three excitons or six particles), whose existence was not obvious because the third exciton spin is unpaired, and the values of their coherence times and binding energies. Rephasing of biexcitons, triexcitons and unbound two-exciton coherences was demonstrated. We also determined that there are no significant unbound correlations of three excitons and no bound or unbound four-exciton (eight-particle) correlations. Thus, the limits, as well as the properties, of many-body correlations in this system were revealed. The measurement methods open a new window into high-order many-body interactions in materials and molecules, and the present results should guide ongoing work on first-principles calculations of electronic interactions in semiconductor nanostructures.

Theory of hydrogen chemisorption on transition metals

Existing theoretical approaches to the description of hydrogen chemisorption on metal surfaces are reviewed. Results from cluster calculations are used to parameterize a model Hamiltonian. Calculations for the binding energy and the adsorbate spectral density arc presented. Special emphasis is given to an examination of the importance of many-body effects upon the description of the chemisorptive bond.

Transport properties of the electron gas in thin AlAs quantum wells: interface-roughness scattering

For interface-roughness scattering and for zero temperature we compare theoretical results for the mobility of the two-dimensional electron gas present in thin AlAs quantum wells with experimental results for a well of width L=45Å. The importance of many-body effects (exchange and correlation) on the mobility is discussed. For the mobility reasonable agreement between theory and experiment is obtained by taking into account a density dependent effective mass and multiple-scattering effects, which lead to a metal-insulator transition.

Screening the Missing Electron: Nanochemistry in Action

The excitement of nano-test-tube chemistry in a single-walled carbon nanotube is exemplified in our study on electron doping in carbon nanotubes. Electron doping through the 1D van Hove singularity of single-walled carbon nanotubes is realized via a chemical reaction of an encapsulated organocerium compound, CeCp3. The decomposition of CeCp3 inside the carbon nanotubes increases the doping level and greatly enhances the density of conduction electrons. The transition of the cerium encapsulating semiconducting tubes to metallic results in enhanced screening of the photoexcited core hole potential. This fact illustrates the importance of many body effects in understanding core-level excitation process in carbon nanotubes.