Accurate and efficient calculations of absorption spectra of molecules and materials are essential for the understanding and rational design of broad classes of systems. Solving the Bethe-Salpeter equation (BSE) for electron-hole pairs usually yields accurate predictions of absorption spectra, but it is computationally expensive, especially if thermal averages of spectra computed for multiple configurations are required. We present a method based on machine learning to evaluate a key quantity entering the definition of absorption spectra: the dielectric screening. We show that our approach yields a model for the screening that is transferable between multiple configurations sampled during first principles molecular dynamics simulations; hence it leads to a substantial improvement in the efficiency of calculations of finite temperature spectra. We obtained computational gains of one to two orders of magnitude for systems with 50 to 500 atoms, including liquids, solids, nanostructures, and solid/liquid interfaces. Importantly, the models of dielectric screening derived here may be used not only in the solution of the BSE but also in developing functionals for time-dependent density functional theory (TDDFT) calculations of homogeneous and heterogeneous systems. Overall, our work provides a strategy to combine machine learning with electronic structure calculations to accelerate first principles simulations of excited-state properties.
The development of new high dielectric materials is essential for advancement in modern electronics. Oxides are generally regarded as the most promising class of high dielectric materials for industrial applications as they possess both high dielectric constants and large band gaps. Most previous researches on high dielectrics were limited to already known materials. In this study, we conducted an extensive search for high dielectrics over a set of ternary oxides by combining crystal structure prediction and density functional perturbation theory calculations. From this search, we adopted mult…
Relaxing the assumption of "infinite and homogenous background" the dielectric response function of one-dimensional (1D) semiconducting nanowires embedded in a dielectric environment is calculated. It is shown that high-k (higher than semiconductor dielectric constant) dielectric environment reduces the screening by the free carriers inside the nanostructure whereas, low dielectric environment increases the Coulombic interaction between free carriers and enhances the strength of screening function. In long wavelength limit, dielectric screening and collective excitation of electron gas are fou…
Two-dimensional (2D) hexagonal boron nitride (BN) nanosheets are excellent dielectric substrate for graphene, molybdenum disulfide and many other 2D nanomaterials based electronic and photonic devices. To optimize the performance of these 2D devices, it is essential to understand the dielectric screening properties of BN nanosheets as a function of the thickness. Here, electric force microscopy along with theoretical calculations based on both state-of-the-art first-principles calculations with van der Waals interactions under consideration and non-linear Thomas-Fermi theory models are used to…
A simple effective screening parameter for screened range-separated hybrid is constructed from the compressibility sum rule in the context of linear-response time-dependent Density Functional Theory. When applied to the dielectric-dependent hybrid (DDH), it becomes remarkably accurate for bulk solids compared to those obtained from fitting with the model dielectric function or depending on the valence electron density of materials. The present construction of the screening parameter is simple and realistic. The screening parameter developed in this way is physically appealing and practically u…
We calculate the long-wavelength static screening properties of both neutral and doped graphene in the framework of density-functional theory. We use a plane-wave approach with periodic images in the third dimension and truncate the Coulomb interactions to eliminate spurious interlayer screening. We carefully address the issue of extracting two dimensional dielectric properties from simulated three-dimensional potentials. We compare this method with analytical expressions derived for two dimensional massless Dirac fermions in the random phase approximation. We evaluate the contributions of the…
We develop a first-principles computational method for investigating the dielectric screening in extended systems using the self-consistent Sternheimer equation and localized non-orthogonal basis sets. Our approach does not require the explicit calculation of unoccupied electronic states, only uses two-center integrals, and has a theoretical scaling of order O(N^3). We demonstrate this method by comparing our calculations for silicon, germanium, diamond, and LiCl with reference planewaves calculations. We show that accuracy comparable to planewaves calculations can be achieved via a systematic…
We reduce the dimensionless interaction strength in graphene by adding a water overlayer in ultra-high vacuum, thereby increasing dielectric screening. The mobility limited by long-range impurity scattering is increased over 30 percent, due to the background dielectric constant enhancement leading to reduced interaction of electrons with charged impurities. However, the carrier-density-independent conductivity due to short range impurities is decreased by almost 40 percent, due to reduced screening of the impurity potential by conduction electrons. The minimum conductivity is nearly unchanged,…
We consider the effect of periodic scalar and vector potentials generated by periodic deformations of the graphene crystal lattice, on the energy spectrum of electrons. The dependence of electron velocity near the Dirac point on the periodic perturbations of different types is discussed. We also investigated the effect of screening of the scalar potential by calculating the dielectric function as a function of the wave length of the periodic potential. This calculation shows that the periodic scalar field is strongly suppressed by the screening. Using the dependence of electron velocity on the…
Moiré superlattices of two-dimensional van der Waals materials have emerged as a powerful platform for designing electronic band structures and discovering emergent physical phenomena. A key concept involves the creation of long-wavelength periodic potential and moiré bands in a crystal through interlayer hybridization when two materials are overlaid. Here we demonstrate a new approach based on spatially periodic dielectric screening to create moiré bands in a monolayer semiconductor. It relies on reduced dielectric screening of the Coulomb interactions in monolayer semiconductors and their en…
Environmental dielectric screening effects on exciton transition energies in single-walled carbon nanotubes (SWNTs) have been studied quantitatively in the range of dielectric constants from 1.0 to 37 by immersing SWNTs bridged over trenches in various organic solvents by means of photoluminescence and the excitation spectroscopies. With increasing environmental dielectric constant ($ε_{\rm env}$), both $E_{11}$ and $E_{22}$ exhibited a redshift by several tens meV and a tendency to saturate at a $ε_{\rm env} \sim 5$ without an indication of significant ($n$,$m$) dependence. The redshifts can …
Various many-body perturbation theory techniques for calculating electron behavior rely on {\it W}, the screened Coulomb interaction. Computing {\it W} requires complete knowledge of the dielectric response of the electronic system, and the fidelity of the calculated dielectric response limits the reliability of predicted electronic and structural properties. As a simplification, calculations often begin with the random-phase approximation (RPA). However, even RPA calculations are costly and scale poorly, typically as $N^4$ ($N$ representing the system size). A local approach has been shown to…
We have studied the dielectric screening of electric field which is induced by a gate voltage in twisted double bilayer graphene by using a sample with a mismatch angle of about 5 degrees. In low temperature magnetotransport measurements, quantum oscillations of magnetoresistance originating from two bands with different carrier density were observed. The behavior of the carrier densities with respect to the total carrier density were distinct from that of the AB-stacked tetralayer graphene. The carrier density ratio was theoretically analyzed in terms of the model that the induced charge deca…
Monolayers of transition-metal dichalcogenides (TMDs) hold great promise as future nanoelectronic and optoelectronic devices. An essential feature for achieving high device performance is the use of suitable supporting substrates, which can affect the electronic and optical properties of these two-dimensional (2D) materials. Here, we perform many-body GW calculations using the SternheimerGW method to investigate the quasiparticle band structure of monolayer MoS2 subject to an effective dielectric screening model, which is meant to approximately describe substrate polarization in real device ap…
We present LayerPCM, an extension of the polarizable-continuum model coupled to real-time time-dependent density-functional theory for an efficient and accurate description of the electrostatic interactions between molecules and multilayered dielectric substrates on which they are physisorbed. The former are modelled quantum-mechanically, while the latter are treated as polarizable continua characterized by their dielectric constants. The proposed approach is purposely designed to simulate complex hybrid heterostructures, with nano-engineered substrates including a stack of anisotropic layers.…
We show that by combining high-k dielectric substrate and high density of charge carriers, Coulomb impurity can be effectively screened, leading to an unprecedented room-temperature mobility of ~150cm2/Vs in monolayer MoS2. The high sample quality enables us to quantitatively extract the mobility components limited by Coulomb impurities, intrinsic and surface optical phonons, and study their scaling with temperature, carrier density and dielectric constant. The excellent agreement between our theoretical analysis and experimental data demonstrates unambiguously that room-temperature phonon-lim…
Above-bandgap femtosecond optical excitation of a ferroelectric/dielectric BaTiO3/CaTiO3 superlattice leads to structural responses that are a consequence of the screening of the strong electrostatic coupling between the component layers. Time-resolved x-ray free-electron laser diffraction shows that the structural response to optical excitation includes a net lattice expansion of the superlattice consistent with depolarization-field screening driven by the photoexcited charge carriers. The depolarization-field-screening-driven expansion is separate from a photoacoustic pulse launched from the…
We use time-dependent density functional theory to calculate the energy loss of an antiproton colliding with a small Al cluster previously excited. The velocity of the antiproton is such that non-linear effects in the electronic response of the Al cluster are relevant. We obtain that an antiproton penetrating an excited cluster transfers less energy to the cluster than an antiproton penetrating a ground state cluster. We quantify this difference and analyze it in terms of the cluster excitation spectrum.
Engineering of the dielectric environment represents a powerful strategy to control the electronic and optical properties of two-dimensional (2D) materials without compromising their structural integrity. Here we show that the recent development of high-$κ$ 2D materials present new opportunities for dielectric engineering. By solving a 2D Mott-Wannier exciton model for WSe$_2$ on different substrates using a screened electron-hole interaction obtained from first principles, we demonstrate that the exciton Rydberg series changes qualitatively when the dielectric screening within the 2D semicond…
We present a general embedding theory of electronic excitations of a relatively small, localized system in contact with an extended, chemically complex environment. We demonstrate how to include the screening response of the environment into highly accurate electronic structure calculation of the localized system by means of an effective interaction between the electrons, which contains only screening processes occurring in the environment. For the common case of a localized system which constitutes an inhomogeneity in an otherwise homogeneous system, such as a defect in a crystal, we show how…
Two-dimensional (2D) materials are increasingly being used as active components in nanoscale devices. Many interesting properties of 2D materials stem from the reduced and highly non-local electronic screening in two dimensions. While electronic screening within 2D materials has been studied extensively, the question still remains of how 2D substrates screen charge perturbations or electronic excitations adjacent to them. Thickness-dependent dielectric screening properties have recently been studied using electrostatic force microscopy (EFM) experiments. However, it was suggested that some of …
The existence of strongly bound excitons is one of the hallmarks of the newly discovered atomically thin semi-conductors. While it is understood that the large binding energy is mainly due to the weak dielectric screening in two dimensions (2D), a systematic investigation of the role of screening on 2D excitons is still lacking. Here we provide a critical assessment of a widely used 2D hydrogenic exciton model which assumes a dielectric function of the form ε(q) = 1 + 2παq, and we develop a quasi-2D model with a much broader applicability. Within the quasi-2D picture, electrons and holes are d…
The screening properties and collective excitations (plasmons) in AA-stacked bilayer graphene are studied within the random phase approximation (RPA). Whereas long lived plasmons in single layer graphene and in AB-stacked bilayer graphene can exist only in doped samples, we find that coherent plasmons can disperse in AA-stacked bilayer graphene {\it even in the absence of doping}. Moreover, we show that the characteristic low energy dispersion relation is unaffected by changes in the number of carriers, unless the chemical potential of the doped sample exceeds the inter-layer hopping energy. W…
We present first-principles many-body calculations of the dielectric constant, quasiparticle band structure, and optical absorption spectrum of monolayer MoS$_2$ using a supercell approach. As the separation between the periodically repeated layers is increased, the dielectric function of the layer develops a strong $q$ dependence around $q=0$. This implies that denser $k$-point grids are required to converge the band gap and exciton binding energies when large supercells are used. In the limit of infinite layer separation, here obtained using a truncated Coulomb interaction, a $45\times45$ $k…
We investigate optical absorption spectra obtained through time-dependent density functional theory (TD-DFT) based on nonempirical hybrid functionals that are designed to correctly reproduce the dielectric function. The comparison with state-of-the-art $GW$ calculations followed by the solution of the Bethe-Sapeter equation (BSE-$GW$) shows close agreement for both the transition energies and the main features of the spectra. We confront TD-DFT with BSE-$GW$ by focusing on the model dielectric function and the local exchange-correlation kernel. The present TD-DFT approach achieves the accuracy…
A Unified Dielectric-Dependent Hybrid Functional for Accurate Band Gaps across Dimensions
Nicolaus Copernicus University in Toruń（托伦哥白尼大学）；Paderborn University（帕德博恩大学）；Indian Institute of Technology, Hyderabad（海德拉巴印度理工学院）；National Institute of Science Education and Research（国家科学教育与研究机构）
Enhanced Screening in Epitaxial Graphene via Nearly Free-Electron Metal Intercalation
Universität Würzburg（维尔茨堡大学）；Würzburg-Dresden Cluster of Excellence ctd.qmat, Universität Würzburg（维尔茨堡大学维尔茨堡-德累斯顿卓越集群ctd.qmat）；Institut für Theoretische Physik und Astrophysik, Universität Würzburg（维尔茨堡大学理论与天体物理研究所）；Diamond Light Source（钻石光源）
We develop a fundamental theory of the long-range electrostatic interactions in two-dimensional crystals by performing a rigorous study of the nonanalyticities of the Coulomb kernel. We find that the dielectric functions are best represented by $2\times 2$ matrices, with nonuniform macroscopic potentials that are two-component hyperbolic functions of the out-of-plane coordinate, $z$. We demonstrate our arguments by deriving the long-range interatomic forces in the adiabatic regime, where we identify a formerly overlooked dipolar coupling involving the out-of-plane components of the dynamical c…
Understanding and controlling properties of plasmon-induced hot carriers is a key step towards next-generation photovoltaic and photocatalytic devices. Here, we uncover a route to engineering hot-carrier generation rates of silver nanoparticles by designed embedding in dielectric host materials. Extending our recently established quantum-mechanical approach to describe the decay of quantized plasmons into hot carriers we capture both external screening by the nanoparticle environment and internal screening by silver d-electrons through an effective electron-electron interaction. We find that h…
All-electron dark matter-electron scattering with random-phase approximation dielectric screening and local field effects
Stony Brook University（石溪大学）；Flatiron Institute（平顿研究所）；C. N. Yang Institute for Theoretical Physics, Stony Brook University（石溪大学杨振宁理论物理研究所）；Institute for Advanced Computational Sciences, Stony Brook University（石溪大学高级计算科学研究院）
The idea of combining different two-dimensional (2D) crystals in van der Waals heterostructures (vdWHs) has led to a new paradigm for band structure engineering with atomic precision. Due to the weak interlayer couplings, the band structures of the individual 2D crystals are largely preserved upon formation of the heterostructure. However, regardless of the details of the interlayer hybridisation, the size of the 2D crystal band gaps are always reduced due to the enhanced dielectric screening provided by the surrounding layers. The effect can be on the order of electron volts, but its precise …
Using a tight-binding Hamiltonian for phosphorene, we have calculated the real part of the polarizability and the corresponding dielectric function, Re$[ε(\textbf{q},ω)]$, at zero temperature (T = 0) with free carrier density $10^{13}$/ $cm^2$. We present results showing the real part of dielectric function in different directions of the transferred momentum $\bf{q}$. When $q$ is larger than a particular value which is twice the Fermi momentum $k_F$, Re$[ε(\textbf{q},ω)]$ becomes strongly dependent on the direction of $\bf{q}$. We also discuss the case at room temperature (T = 300K). These res…
The competition between the electron-hole Coulomb attraction and the three-dimensional dielectric screening dictates the optical properties of layered semiconductors. In low-dimensional materials, the equilibrium dielectric environment can be significantly altered by the ultrafast excitation of photo-carriers, leading to renormalized band gap and exciton binding energies. Recently, black phosphorus emerged as a 2D material with strongly layer-dependent electronic properties. Here, we resolve the coherent response of screening to sub-gap photo-excitation in bulk black phosphorus and find that m…
We perform high-throughput density functional theory (DFT) calculations for optoelectronic properties (electronic bandgap and frequency dependent dielectric function) using the OptB88vdW functional (OPT) and the Tran-Blaha modified Becke Johnson potential (MBJ). This data is distributed publicly through JARVIS-DFT database. We used this data to evaluate the differences between these two formalisms and quantify their accuracy, comparing to experimental data whenever applicable. At present, we have 17,805 OPT and 7,358 MBJ bandgaps and dielectric functions. MBJ is found to predict better bandgap…
We calculate the dielectric response of excited crystalline silicon in electron thermal equilibrium by adiabatic time-dependent density functional theory (TDDFT) to model the response to irradiation by high-intensity laser pulses. The real part of the dielectric function is characterized by the strong negative behavior at low frequencies due to excited electron-hole pairs. The response agrees rather well with the numerical pump-probe calculations which simulate electronic excitations in nonequilibrium phase immediately after the laser pulse irradiation. The thermal response is also compared wi…
We investigate the effects of environmental dielectric screening on the electronic dispersion and the band gap in the atomically-thin, quasi two-dimensional (2D) semiconductor WS$_2$ using correlative angle-resolved photoemission and optical spectroscopies, along with first-principles calculations. We find the main effect of increased environmental screening to be a reduction of the band gap, with little change to the electronic dispersion of the band structure. These essentially rigid shifts of the bands results from the special spatial structure of the changes in the Coulomb potential induce…
Luttinger semimetals are three-dimensional electron systems with a parabolic band touching and an effective total spin $J=3/2$. In this paper, we present an analytical theory of dielectric screening of inversion-symmetric Luttinger semimetals with an arbitrary carrier density and conduction-valence effective mass asymmetry. Assuming a spherical approximation for the single-particle Luttinger Hamiltonian, we determine analytically the dielectric screening function in the random phase approximation for arbitrary values of the wave vector and frequency, the latter in the complex plane. We use thi…
We investigate spectral behavior of phonon spectral functions in an interacting multi-component hot carrier plasma. Dielectric polarization functions are formulated so that they satisfy Dyson equations of the effective interactions among plasma components. We find a useful sum rule giving simple relation between plasma-species resolved dielectric functions. Spectral analysis of various phonon spectral functions is performed considering carrier-phonon channels of polar and nonpolar optical phonons, acoustic deformation-potential, and piezoelectric Coulomb couplings. Effects of phonon self-energ…
Physics-Based Factorized Machine Learning for Predicting Ionic Dielectric Tensors
Institute for Materials Research, Tohoku University（东北大学物质材料研究机构）；Graduate School of Engineering, Tohoku University（东北大学大学院工学研究科）；Organization for Advanced Studies, Tohoku University（东北大学先进教育研究机构）
The manipulation of two-dimensional materials via their dielectric environment offers novel opportunities to control electronic as well as optical properties and allows to imprint nanostructures in a non-invasive way. Here we asses the potential of monolayer semiconducting transition metal dichalcogenides (TMDCs) for Coulomb engineering in a material realistic and quantitative manner. We compare the response of different TMDC materials to modifications of their dielectric surrounding, analyze effects of dynamic substrate screening, i.e. frequency dependencies in the dielectric functions, and d…
One of the main sources of error associated with the calculation of defect formation energies using plane-wave Density Functional Theory (DFT) is finite size error resulting from the use of relatively small simulation cells and periodic boundary conditions. Most widely-used methods for correcting this error, such as that of Makov and Payne, assume that the dielectric response of the material is isotropic and can be described using a scalar dielectric constant $ε$. However, this is strictly only valid for cubic crystals, and cannot work in highly-anisotropic cases. Here we introduce a variation…
The electronic structure of two-dimensional (2D) materials are inherently prone to environmental perturbations, which may pose significant challenges to their applications in electronic or optoelectronic devices. A 2D material couples with its environment through two mechanisms: local chemical coupling and nonlocal dielectric screening effects. The local chemical coupling is often difficult to predict or control experimentally. Nonlocal dielectric screening, on the other hand, can be tuned by choosing the substrates or layer thickness in a controllable manner. Therefore, a compelling 2D electr…
We calculate the dielectric response of crystalline silicon following irradiation by a high-intensity laser pulse, modeling the dynamics by time-dependent density functional theory (TDDFT). The pump-probe measurements are numerically simulated by solving the time-dependent Kohn-Sham equation with the pump and probe fields included as external fields. As expected, the excited silicon shows features of a particle-hole plasma in its response. We compare the calculated response with a thermal model and with a simple Drude model. The thermal model requires only a static DFT calculation to prepare e…
The dielectric constant, which defines the polarization of the media, is a key quantity in condensed matter. It determines several electronic and optoelectronic properties important for a plethora of modern technologies from computer memory to field effect transistors and communication circuits. Moreover, the importance of the dielectric constant in describing electromagnetic interactions through screening plays a critical role in understanding fundamental molecular interactions. Here we show that despite its fundamental transcendence, the dielectric constant does not define unequivocally the …
Exciton dissociation at heterojunctions in photovoltaic devices is not completely understood despite being fundamentally necessary to generate electrical current. One of the fundamental issues for ab initio calculations is that hybrid interfaces combining materials with Wannier-Mott excitons and those with Frenkel excitons can easily require thousands of atoms to encompass the exciton-wave function. The problem is further exacerbated by a large permittivity difference at the interface, which requires meso-scale boundary conditions to accurately predict electrostatic potentials. For these reaso…
Two-dimensional (2D) materials are outstanding platforms for exotic physics and emerging applications by forming interfaces. In order to efficiently take into account the substrate screening in the quasiparticle energies of 2D materials, several theoretical methods have been proposed previously, but only applicable to interfaces of two systems' lattice constants with certain integer proportion. In this work, we analytically showed the equivalence and distinction among different approximate methods for substrate dielectric matrices. We evaluated the accuracy of these methods, by applying them t…
