Many-body Effects Research Articles

Many-body effects in machine-learned molecular surface predictions

Many-body effects in machine-learned molecular surface predictions

Spatially-indirect and hybrid exciton–exciton interaction in MoS2 homobilayers

Interlayer excitons in transition-metal dichalcogenide (TMD) bilayers, alongside their interplay with direct excitonic species, are supposed to offer a pathway towards robust nonlinearity, enabling the exploration of many-body quantum effects. We present a theoretical investigation of interaction among various exciton species within these structures where Coulomb attraction and repulsion are subject to reduced screening. For a homobilayer MoS2, we examine both direct, spatially-indirect, and hybridised excitons, considering the effects of direct and exchange interaction of electrons and holes distributed across one or different layers. Similar physics arises in perfectly aligned twisted TMD heterobilayers which support the direct-to-indirect exciton hybridisation. Deriving the exciton–exciton interaction matrix elements, we unveil a distinct non-monotonic dependence of the interaction on transferred momentum, changing sign from repulsive to attractive even for ground-state excitons, and compare our results with existing calculations for monolayers. Our findings demonstrate that for large momenta involved in high-density effects (strongly correlated phases), the interaction is chiefly governed by the prevailing attractive exchange component. At the same time, at small momenta that are more relevant for rarefied systems, we find that the enhancement of the interaction constant for dipolar species compared to intralayer non-dipolar excitons may be hindered by the surrounding medium. We draw comparisons with existing experiments and discuss the implications of our findings on the collective effects in TMD-based systems of excitons and exciton-polaritons.

A many-body energy decomposition analysis (MB-EDA) scheme based on a target state optimization self-consistent field (TSO-SCF) method.

In this paper, we combine an energy decomposition analysis (EDA) scheme with many-body expansion (MBE) to develop a MB-EDA method to study the cooperative and anti-cooperative effects in molecular cluster systems. Based on the target state optimization self-consistent field (TSO-SCF) method, the intermolecular interaction energy can be decomposed into five chemically meaningful terms, i.e., electrostatic, exchange, polarization, charge transfer and dispersion interaction energies. MB-EDA can decompose each of these terms in MBE. This MB-EDA has been applied to 3 different cluster systems: water clusters, ionic liquid clusters, and acetonitrile-methane clusters. This reveals that electrostatic, exchange, and dispersion interactions are highly pairwise additive in all systems. In water and ionic liquid clusters, the many-body effects are significant in both polarization and charge transfer interactions, but are cooperative and anti-cooperative, respectively. For acetonitrile-methane clusters, which do not involve hydrogen bonds or charge-charge Coulombic interactions, the many-body effects are quite small. The chemical origins of different many-body effects are deeply analyzed. The MB-EDA method has been implemented in Qbics (https://qbics.info) and can be a useful tool for understanding the many-body behavior in molecular aggregates at the quantum chemical level of theory.

Selective Damping of Plasmons in Coupled Two-Dimensional Systems by Coulomb Drag

The Coulomb drag is a many-body effect observed in proximized low-dimensional systems. It appears as emergence of voltage in one of them upon passage of bias current in another. The magnitude of drag voltage can be strongly affected by exchange of plasmonic excitations between the layers; however, the reverse effect of Coulomb drag on properties of plasmons has not been studied. Here, we study the plasmon spectra and damping in parallel two-dimensional systems in the presence of Coulomb drag. We find that Coulomb drag leads to selective damping of one of the two fundamental plasma modes of a coupled bilayer. For identical electron doping of both layers, the drag suppresses the acoustic plasma mode; while for symmetric electron-hole doping of the coupled pair, the drag suppresses the optical plasma mode. The selective damping can be observed both for propagating modes in extended bilayers and for localized plasmons in bilayers confined by source and drain contacts. The discussed effect may provide access to the strength of Coulomb interaction in 2d electron systems from various optical and microwave scattering experiments.

Electronic correlations and intrinsic magnetism of interstitial quasi-atomic states in Li8Au electride.

We investigate the electronic sub-system of a recently designed Li8Au superconducting electride to reveal its many-body correlated nature and magnetic properties. Using maximally localized Wannier functions (MLWFs) to describe the interstitial anion electron (IAE) states, it was found that these states are partially occupied with a population of 1.5e- and have negligible hybridization with the almost completely filled p-Au states. The averaged interaction screened Hubbard parameter U for quasi-atomic IAE states evaluated by the constrained random-phase approximation (CRPA) method is 2 eV, comparable to the width of the electride band suggesting moderate electronic correlations. Using dynamical mean field theory (DMFT) approach we found that IAEs in Li8Au electride behave as magnetic centers and possess their own well localised magnetic moments of 0.5μB per quasi-atomic IAE. The obtained results deepen the understanding of the significance of many-body effects in the IAE subsystem of electronic states and reveal the mechanism for the formation of intrinsic magnetic moments on IAEs, which behave like ferromagnetic quasi-atoms in the Li8Au electride. Overall, the observed correlation effects in Li8Au emphasize their importance in materials with excess electrons confined in cavities.

Insights into the optoelectronic behaviour of heteroatom doped diamond-shaped graphene quantum dots.

In this study we aim to manipulate the optoelectronic and photoluminescence properties of diamond-shaped graphene quantum dots (DSGQDs) in order to make them suitable for solar cells and photovoltaic devices. Using DFT and performing many-body effects studies, we investigate the impact of N, B, O, P and S heteroatom doping on DSGQDs in three different positions, namely the zigzag edge, the armchair corner and the surface, in order to identify the most appropriate and promising configurations. All the doped GQDs are found to be chemically stable making it possible to realize them experimentally. Additionally, the obtained results show that substitution with heteroatoms has a remarkable effect on the electronic energy gap, noticeably decreasing it. Doping also has a significant effect on the optical response by shifting the absorption peaks towards the visible energy range. The excitonic behaviour has revealed that these nanostructures are potential candidates for photovoltaic devices. One can deduce that doping DSGQDs with heteroatoms is useful and promising for the targeted applications.

Water-glycan interactions drive the SARS-CoV-2 spike dynamics: insights into glycan-gate control and camouflage mechanisms.

To develop therapeutic strategies against COVID-19, we introduce a high-resolution all-atom polarizable model capturing many-body effects of protein, glycan, solvent, and membrane components in SARS-CoV-2 spike protein open and closed states. Employing μs-long molecular dynamics simulations powered by high-performance cloud-computing and unsupervised density-driven adaptive sampling, we investigated the differences in bulk-solvent-glycan and protein-solvent-glycan interfaces between these states. We unraveled a sophisticated solvent-glycan polarization interaction network involving the N165/N343 glycan-gate patterns that provide structural support for the open state and identified key water molecules that could potentially be targeted to destabilize this configuration. In the closed state, the reduced solvent polarization diminishes the overall N165/N343 dipoles, yet internal interactions and a reorganized sugar coat stabilize this state. Despite variations, our glycan-solvent accessibility analysis reveals the glycan shield capability to conserve constant interactions with the solvent, effectively camouflaging the virus from immune detection in both states. The presented insights advance our comprehension of viral pathogenesis at an atomic level, offering potential to combat COVID-19.

On silicon nanobubbles in space for scattering and interception of solar radiation to ease high-temperature induced climate change

A thin film of silicon-based nanobubbles was recently suggested that could block a fraction of the sun’s radiation to alleviate the present climate crisis. But detailed information is limited to the composition, architecture, fabrication, and optical properties of the film. We examine here the optical response of Si nanobubbles in the range of 300–1000 nm to evaluate the feasibility using semi numerical solution of Maxwell’s equations, following the Mie and finite-difference time-domain procedures. We analyzed a variety of bubble sizes, thicknesses, and configurations. The calculations yield resonance scattering spectra, intensities, and field distributions. We also analyzed some many-body effects using doublets of bubbles. We show, due to high valence electron density, silicon exhibits strong polarization/plasmonic resonance scattering and absorption enhancements over the geometrical factor, which afford lighter but more efficient interception with a wide band neutral density filtering across the relevant solar light spectrum. We show that it is sufficient to use a sub monolayer raft with ∼0.75% coverage, consisting of thin (∼15 nm) but large silicon nanobubbles (∼550 nm diameter), to achieve 1.8% blockage of solar light with neutral density filtering, and ∼0.78 mg/m2 silicon, much less than the mass effective limit set earlier at 1.5 g/m2. We evaluated solid counterpart nanoparticles, which may be produced in blowing/inflation procedures of molten silicon, as well as aging by including silicon oxide capping. The studies confirm the feasibility of a space bubble filtering raft, with insignificant imbalance of the correlated color temperature (CCT) and color rendering index characteristics of sunlight.

Understanding the emergence of negative photoconductivity in CVD grown ReS2 thin films by invoking the trion generation mechanism.

Emerging from robust coulombic interactions and diminished dielectric screening, two-dimensional transition metal dichalcogenides (2D TMDs) manifest strongly bound excitons. While these pronounced many-body effects have been observed in 2D TMDs, their impact on the materials' intrinsic photoconductive characteristics remains relatively less explored. In this study, a considerable reduction in photoconductivity in chemical vapor deposited (CVD) ReS2 thin films has been observed. Through experimental and theoretical scrutiny, it is deduced that this anomalous phenomenon stems from the possible many-body interactions within the system, wherein photoexcited electron-hole pairs combine with excess electrons to generate trions. The formation of trions reduces the effective number of carriers contributing to photocurrent, thereby attenuating the photoconductivity. This study shows the profound influence of trions on the photoconductivity behaviour of ReS2 thin films, thereby elucidating their significance in modulating optical and electrical properties crucial for optoelectronic applications.

Excitonic Effects in Energy-Loss Spectra of Freestanding Graphene.

In this work, we perform electron energy-loss spectroscopy (EELS) of freestanding graphene with high energy and momentum resolution to disentangle the quasielastic scattering from the excitation gap of Dirac electrons close to the optical limit. We show the importance of many-body effects on electronic excitations at finite transferred momentum by comparing measured EELS to ab initio calculations at increasing levels of theory. Quasi-particle corrections and excitonic effects are addressed within the GW approximation and the Bethe-Salpeter equation, respectively. Both effects are essential in the description of the EEL spectra to obtain a quantitative agreement with experiments, with the position, dispersion, and shape of both the excitation gap and the π plasmon being significantly affected by excitonic effects.

Tipping the Balance Between the bcc and fcc Phase Within the Alkali and Coinage Metal Groups.

Why the Group 1 elements crystallize in the body-centered cubic (bcc) structure, and the iso-electronic Group 11 elements in the face-centered cubic (fcc) structure, remains a mystery. Here we show that a delicate interplay between many-body effects, vibrational contributions and dispersion interactions obtained from relativistic density functional theory offers an answer to this long-standing controversy. It also sheds light on the Periodic Table of Crystal Structures. A smooth diffusionless transition through cuboidal lattices gives a detailed insight into the bcc→fcc phase transition for the Groups 1 and 11 elements.

Optical manipulation of the topological phase in ZrTe5 revealed by time- and angle-resolved photoemission

High-resolution time- and angle-resolved photoemission measurements were conducted on the topological insulator ZrTe5. With strong femtosecond photoexcitation, a possible ultrafast phase transition from a weak to a strong topological insulating phase was experimentally realized by recovering the energy gap inversion in a time scale that was shorter than 0.15 ps. This photoinduced transient strong topological phase can last longer than 2 ps at the highest excitation fluence studied, and it cannot be attributed to the photoinduced heating of electrons or modification of the conduction band filling. Additionally, the measured unoccupied electronic states are consistent with the first-principles calculation based on experimental crystal lattice constants, which favor a strong topological insulating phase. These findings provide new insights into the longstanding controversy about the strong and weak topological properties in ZrTe5, and they suggest that many-body effects including electron–electron interactions must be taken into account to understand the equilibrium weak topological insulating phase in ZrTe5.

Spin-Stabilization by Coulomb Blockade in a Vanadium Dimer in WSe2.

Charged dopants in 2D transition metal dichalcogenides (TMDs) have been associated with the formation of hydrogenic bound states, defect-bound trions, and gate-controlled magnetism. Charge-transfer at the TMD-substrate interface and the proximity to other charged defects can be used to regulate the occupation of the dopant's energy levels. In this study, we examine vanadium-doped WSe2 monolayers on quasi-freestanding epitaxial graphene, by high-resolution scanning probe microscopy and ab initio calculations. Vanadium atoms substitute W atoms and adopt a negative charge state through charge donation from the graphene substrate. VW-1 dopants exhibit a series of occupied p-type defect states, accompanied by an intriguing electronic fine-structure that we attribute to hydrogenic states bound to the charged impurity. We systematically studied the hybridization in V dimers with different separations. For large dimer separations, the 2e- charge state prevails, and the magnetic moment is quenched. However, the Coulomb blockade in the nearest-neighbor dimer configuration stabilizes a 1e- charge state. The nearest-neighbor V-dimer exhibits an open-shell character for the frontier defect orbital, giving rise to a paramagnetic ground state. Our findings provide microscopic insights into the charge stabilization and many-body effects of single dopants and dopant pairs in a TMD host material.

Enhanced optical conductivity and many-body effects in strongly-driven photo-excited semi-metallic graphite

The excitation of quasi-particles near the extrema of the electronic band structure is a gateway to electronic phase transitions in condensed matter. In a many-body system, quasi-particle dynamics are strongly influenced by the electronic single-particle structure and have been extensively studied in the weak optical excitation regime. Yet, under strong optical excitation, where light fields coherently drive carriers, the dynamics of many-body interactions that can lead to new quantum phases remain largely unresolved. Here, we induce such a highly non-equilibrium many-body state through strong optical excitation of charge carriers near the van Hove singularity in graphite. We investigate the system’s evolution into a strongly-driven photo-excited state with attosecond soft X-ray core-level spectroscopy. We find an enhancement of the optical conductivity of nearly ten times the quantum conductivity and pinpoint it to carrier excitations in flat bands. This interaction regime is robust against carrier-carrier interaction with coherent optical phonons acting as an attractive force reminiscent of superconductivity. The strongly-driven non-equilibrium state is markedly different from the single-particle structure and macroscopic conductivity and is a consequence of the non-adiabatic many-body state.

Measurement of polarization transfer in the quasi-elastic [formula omitted] process

Polarization transfer to a bound proton in polarized electron knock-out reactions, A(e→,e′p→), is a powerful tool to look for an in-medium modification of the bound proton. It requires comparison to calculations that consider the many-body effects accompanying the quasi-free process. We report here measured components Px′, Pz′, and their ratio Px′/Pz′, of polarization transfer to protons bound in Ca40, which is described well by the shell model and for which reliable calculations are available. While the calculations capture the essence of the data, our statistical precision allows us to observe deviations that cannot be explained by simple scaling, including by varying the proton electromagnetic form factor ratio GE/GM. We further explore the deviations of the ratio of the polarization transfer components from that of a free proton, (Px′/Pz′)A/(Px′/Pz′)H, and its dependence on the bound-proton virtuality.

Landau levels for a Weyl pair in a monolayer medium and thermal quantities

In this paper, we consider a Weyl pair under the effect of an external uniform magnetic field in a monolayer medium without considering any charge-charge interaction between the particles. Choosing the interaction of the particles with the magnetic field in the symmetric gauge we seek for an analytical solution of the corresponding form of a one-time fully-covariant two-body Dirac equation derived from quantum electrodynamics via the action principle. As it is usual with two-body problems, we separate the relative motion and center of mass motion coordinates. Assuming the center of mass is at rest, we derive a matrix equation in terms of the relative motion coordinates without considering any group theoretical method. This equation gives a wave equation in exactly soluble form and accordingly we obtain the spinor components and complete energy eigen-states (in closed form) for such a spinless composite structure. Our results not only give exact Landau levels for such a Weyl pair in a monolayer medium but also show the considered system behaves as a two-dimensional harmonic oscillator. Furthermore, our findings give exactly the excited states of a Weyl particle under the effect of uniform external magnetic field in a monolayer graphene sheet and there is no imprint to distinguish these modes from each other. This means that the performed experiments based on Landau levels for a monolayer graphene sheet may actually involve many-body effects. Our results provide a suitable basis to analyze the associated thermal quantities and accordingly we discuss the thermal properties by determining free energy, total energy, entropy and specific heat for the composite system in question.

Electron–phonon interaction and electronic correlations in transport through electrostatically and tunnel coupled quantum dots

We investigate two equivalent capacitively and tunnel coupled quantum dots, each coupled to its own pair of leads. Local Holstein type electron–phonon coupling at the dots is assumed. To study many-body effects we use the finite-U mean-field slave boson approach. For vanishing interdot interaction, weak e–ph coupling and finite tunneling, molecular orbital spin Kondo effects occur for single electron or single hole occupations. Phonons influence both correlations and tunneling and additionally they shift the energies of the dots. Depending on the dot energies and the strength of electron–phonon coupling, the system is occupied by a different number of electrons that effectively interact with each other repulsively or attractively leading to a number of different ground states of DQD. Among them are Kondo-like states with spin, orbital or charge correlations resulting from polaron cotunneling processes and states with magnetic intersite correlations.

Cooperativity and Frustration Effects (or Lack Thereof) in Polarizable and Non-polarizable Force Fields.

Understanding cooperativity and frustration is crucial for studying biological processes such as molecular recognition and protein aggregation. Force fields have been extensively utilized to explore cooperativity in the formation of protein secondary structures and self-assembled systems. Multiple studies have demonstrated that polarizable force fields provide more accurate descriptions of this phenomenon compared to fixed-charge pairwise nonpolarizable force fields, thanks to the incorporation of polarization effects. In this study, we assess the performance of the AMOEBA polarizable force field and the AMBER and OPLS nonpolarizable pairwise force fields in capturing positive and negative cooperativity recently explored in neutral and charged molecular clusters using density functional theory. Our findings show that polarizable and nonpolarizable force fields qualitatively reproduce the relative cooperativity observed in electron structure calculations. However, AMBER and OPLS fail to describe absolute cooperativity. In contrast, AMOEBA accounts for the absolute cooperativity by considering interactions beyond pairwise interactions. According to the energy decomposition analysis, it is observed that the electrostatic interactions calculated with the AMBER and OPLS force fields seem to play an important and counterintuitive role in reproducing the adiabatic interaction energies calculated with density functional theory. However, it is important to note that these force fields, due to their nature, do not explicitly incorporate many-body effects, which limits their ability to accurately describe cooperativity. On the other hand, frustration in polarizable and nonpolarizable force fields is caused by changes in bond stretching and angle bending terms of the building blocks when they are forming a complex.

Enhanced Exciton Drift Transport through Suppressed Diffusion in One-Dimensional Guides.

Drift-diffusion dynamics is investigated in a one-dimensional (1D) exciton guide at room temperature. Spatial engineering of the exciton energy in a WSe2 monolayer is achieved using local strain to confine and direct exciton transport. An unexpected and massive deviation from the Einstein relation is observed and correlated to exciton capture by defects. We find that the capture reduces exciton temperature and diffusion so much that drift transport visibility improves to 38% as excitons traverse asymmetrically over regions with occupied defect states. Based on measurements over multiple potential gradients, we estimate the exciton mobility to be 169 ± 39 cm2/(eV s) at room temperature. Experiments at elevated exciton densities reveal that the exciton drift velocity monotonically increases with exciton density, unlike exciton mobility, due to contributions from nonequilibrium many-body effects.

Many-body non-Hermitian skin effect at finite temperatures

Many-body non-Hermitian skin effect at finite temperatures