Ab Initio Many-body Perturbation Theory Research Articles

Exciton-Phonon Coupling Induces a New Pathway for Ultrafast Intralayer-to-Interlayer Exciton Transition and Interlayer Charge Transfer in WS2-MoS2 Heterostructure: A First-Principles Study.

Despite the weak, van der Waals interlayer coupling, photoinduced charge transfer vertically across atomically thin interfaces can occur within surprisingly fast, sub-50 fs time scales. An early theoretical understanding of charge transfer is based on a noninteracting picture, neglecting excitonic effects that dominate optical properties of such materials. We employ an ab initio many-body perturbation theory approach, which explicitly accounts for the excitons and phonons in the heterostructure. Our large-scale first-principles calculations directly probe the role of exciton-phonon coupling in the charge dynamics of the WS2/MoS2 heterobilayer. We find that the exciton-phonon interaction induced relaxation time of photoexcited excitons at the K valley of MoS2 and WS2 is 67 and 15 fs at 300 K, respectively, which sets a lower bound to the intralayer-to-interlayer exciton transfer time and is consistent with experiment reports. We further show that electron-hole correlations facilitate novel transfer pathways that are otherwise inaccessible to noninteracting electrons and holes.

Noise-independent route toward the genesis of a COMPACT ansatz for molecular energetics: A dynamic approach.

Recent advances in quantum information and quantum science have inspired the development of various compact, dynamically structured ansätze that are expected to be realizable in Noisy Intermediate-Scale Quantum (NISQ) devices. However, such ansätze construction strategies hitherto developed involve considerable measurements, and thus, they deviate significantly in the NISQ platform from their ideal structures. Therefore, it is imperative that the usage of quantum resources be minimized while retaining the expressivity and dynamical structure of the ansatz that can adapt itself depending on the degree of correlation. We propose a novel ansatz construction strategy based on the abinitio many-body perturbation theory that requires no pre-circuit measurement and, thus, remains structurally unaffected by any hardware noise. The accuracy and quantum complexity associated with the ansatz are solely dictated by a pre-defined perturbative order, as desired, and, hence, are tunable. Furthermore, the underlying perturbative structure of the ansatz construction pipeline enables us to decompose any high-rank excitation that appears in higher perturbative orders into the product of various low-rank operators, and it thus keeps the execution gate-depth to its minimum. With a number of challenging applications on strongly correlated systems, we demonstrate that our ansatz performs significantly better, both in terms of accuracy, parameter count, and circuit depth, in comparison to the allied unitary coupled cluster based ansätze.

Band splitting under strain: A route to broad-spectrum absorption

A strategy to split bright exciton bands is proposed to achieve broad-spectrum absorption in two-dimensional semiconductors. Based on ab initio many-body perturbation theory and Bethe-Salpeter equation calculations, we predict that post-transition-metal chalcogenides monolayers can realize broadband absorption under biaxial tensile strains. We find that top valence bands responsible for the strongly absorbing excitons exhibit disparate bonding characteristics and symmetries, thus responding to the strain differently. A moderate strain on the monolayers could yield large energy splitting of the exciton bands and a redshift of the band gap, broadening the absorption across the solar spectrum. The bright excitons have mixed inter- and intra-layer features, rendering them with relatively long lifetimes and strong absorption amplitudes. This work provides a new perspective to engineer two-dimensional materials with superior optoelectronic properties.

Chemical Mapping of Excitons in Halide Double Perovskites.

Halide double perovskites comprise an emerging class of semiconductors with tremendous chemical and electronic diversity. While their band structure features can be understood from frontier-orbital models, chemical intuition for optical excitations remains incomplete. Here, we use ab initio many-body perturbation theory within the GW and the Bethe-Salpeter equation approach to calculate excited-state properties of a representative range of Cs2BB'Cl6 double perovskites. Our calculations reveal that double perovskites with different combinations of B and B' cations display a broad variety of electronic band structures and dielectric properties and form excitons with binding energies ranging over several orders of magnitude. We correlate these properties with the orbital-induced anisotropy of charge-carrier effective masses and the long-range behavior of the dielectric function by comparing them with the canonical conditions of the Wannier-Mott model. Furthermore, we derive chemically intuitive rules for predicting the nature of excitons in halide double perovskites using computationally inexpensive density functional theory calculations.

Optical Tunable Moiré Excitons in Twisted Hexagonal GaTe Bilayers

Optical fine-tunable layer-hybridized Moiré excitons are highly in demand for emerging many-body states in two-dimensional semiconductors. We report naturally confined layer-hybridized bright Moiré excitons with long lifetimes in twisted hexagonal GaTe bilayers, using ab initio many-body perturbation theory and the Bethe–Salpeter equation. Due to the hybridization of electrons and holes between layers, which enhances the brightness of excitons, the twisted bilayer system becomes attractive for optical applications. We find that in both R and H-type stacking Moiré superlattices, more than 200 meV lateral quantum confinements occur on exciton energies, which results in two scenarios: (1) The ground state bright excitons XA are found to be trapped at two high-symmetry points, with opposite electric dipoles in the R-stacking Moiré supercell, forming a honeycomb superlattice of nearest-neighbor dipolar attraction. (2) For H-stacking case, the XA is found to be trapped at only one high-symmetry point exhibiting a triangular superlattice. Our results suggest that twisted h-GaTe bilayer is one of the promising systems for optical fine-tunable excitonic devices and provide an ideal platform for realizing strong correlated Bose–Hubbard physics.

Optical, electronic, and structural properties of ScAlMgO4

Magnesium aluminate scandium oxide (ScAlMgO4) is a promising lattice-matched substrate material for GaN- and ZnO-based optoelectronic devices. Yet, despite its clear advantages over substrates commonly used in heteroepitaxial growth, several fundamental properties of ScAlMgO4 remain unsettled. Here, we provide a comprehensive picture of its optical, electronic and structural properties by studying ScAlMgO4 single crystals grown by the Czochralski method. We use variable angle spectroscopic ellipsometry to determine complex in-plane and out-of-plane refractive indices in the range from 193 to 1690 nm. An oscillator-based model provides a phenomenological description of the ellipsometric spectra with excellent agreement over the entire range of wavelengths. For convenience, we supply the reader also with Cauchy formulas describing the real part of the anisotropic refractive index for wavelengths above 400 nm. Ab initio many-body perturbation theory modeling provides information about the electronic structure of ScAlMgO4, and successfully validated experimentally obtained refractive index values. Simulations also show exciton binding energy as large as a few hundred of meV, indicating ScAlMgO4 as a promising material for implementation in low-threshold, deep-UV lasing devices operating at room temperature. X-ray diffraction measurements confirm lattice constants of ScAlMgO4 previously reported, but in addition, reveal that dominant crystallographic planes (001) are mutually inclined by about 0.009{\deg}. In view of our work, ScAlMgO4 is a highly transparent, low refractive index, birefringent material similar to a sapphire, but with a much more favorable lattice constant and simpler processing.

Origin of contact polarity at metal-2D transition metal dichalcogenide interfaces

Using state-of-the-art ab initio GW many-body perturbation theory calculations, we show that monolayer MoS2 on Au is a p-type contact, in contrast to the vast majority of theoretical predictions using density functional theory. The predominantly n-type behaviour observed experimentally for MoS2/Au junctions can be attributed to the presence of sulfur vacancies, which pin the Fermi level. GW calculations on WSe2/Au junctions likewise predict p-type contacts for pristine WSe2 and n-type contacts for junctions with selenium vacancies. Experimentally, WSe2/metal junctions are predominantly p-type or ambipolar, with p-type junctions being observed for selenium-deficient WSe2, suggesting that selenium vacancies are not effective in pinning the Fermi level for WSe2/metal junctions. We rationalize these apparently contradictory results by noting that selenium vacancies in WSe2 are readily passivated by oxygen atoms. Taken together, our state-of-the-art calculations clearly elucidate the relation between contact polarity and atomic structure. We show that non-local exchange and correlation effects are critical for determining the energy level alignment and even the contact polarity (in the case of MoS2 on Au). We further reconcile a large body of experimental literature on TMDC/metal contact polarities by consideration of the defect chemistry.

Bethe-Salpeter equation insights into the photo-absorption function and exciton structure of chlorophyll a and b in light-harvesting complex II.

The photo-absorption process and the excitation of chlorophyll (Chl) is the primary and essential step of photosynthesis in green plants. By solving the Bethe-Salpeter equation (BSE) on top of the GW approximation within ab initio many-body perturbation theory, we calculate the photo-absorption function and the excitons structure of Chl a and b in their in vivo conformations as measured by X-ray diffraction in the light-harvesting complex (LHC) II. BSE optical absorption spectra are in good agreement with the experiment and we discuss residual discrepancies. The experimental evidence of multiple Chla forms in vivo is explained by BSE. The Chla and Chlb BSE exciton wavefunctions present important charge-transfer differences on the Soret band. Q excitons are almost identical, apart from charge (both electron and hole) localization on the Chlb C7 aldheide formyl group, absent on the Chla methyl C7, that is exactly the group where the two chlorophylls differ.

Fragment-orbital-dependent spin fluctuations in the single-component molecular conductor [Ni(dmdt)2]

Motivated by recent nuclear magnetic resonance experiments, we calculated the spin susceptibility, Knight shift, and spin-lattice relaxation rate ($1/T_{1}T$) of the single-component molecular conductor [Ni(dmdt)$_2$] using the random phase approximation in a multi-orbital Hubbard model describing the Dirac nodal line electronic system in this compound. This Hubbard model is composed of three fragment orbitals and on-site repulsive interactions obtained using ab initio many-body perturbation theory calculations. We found fragment-orbital-dependent spin fluctuations with the momentum $\textbf{q}$=$\textbf{0}$ and an incommensurate value of the wavenumber $\textbf{q}$=$\textbf{Q}$ at which a diagonal element of the spin susceptibility is maximum. The $\textbf{q}$=$\textbf{0}$ and $\textbf{Q}$ responses become dominant at low and high temperatures, respectively, with the Fermi-pocket energy scale as the boundary. We show that $1/T_{1}T$ decreases with decreasing temperature but starts to increase at low temperature owing to the $\textbf{q}$=$\textbf{0}$ spin fluctuations, while the Knight shift keeps monotonically decreasing. These properties are due to the intra-molecular antiferromagnetic fluctuations caused by the characteristic wave functions of this Dirac nodal line system, which is described by an $n$-band ($n\geq 3$) model. We show that the fragment orbitals play important roles in the magnetic properties of [Ni(dmdt)$_2$].

Optimally tuned starting point for single-shotGWcalculations of solids

The dependence of ab initio many-body perturbation theory within the $GW$ approximation on the eigensystem used in calculating quasiparticle corrections limits this method's predictive power. Here, we investigate the accuracy of the recently developed Wannier-localized optimally tuned screened range-separated hybrid (WOT-SRSH) functional as a generalized Kohn-Sham starting point for single-shot $GW$ ($G_0W_0$) calculations for a range of semiconductors and insulators. Comparison to calculations based on well-established functionals, namely PBE, PBE0, and HSE, as well as to self-consistent $GW$ schemes and to experiment, shows that band gaps computed via $G_0W_0$@WOT-SRSH have a level of precision and accuracy that is comparable to that of more advanced methods such as quasiparticle self-consistent $GW$ (QS$GW$) and eigenvalue self-consistent $GW$ (ev$GW$). We also find that $G_0W_0$@WOT-SRSH improves the description of states deeper in the valence band manifold. Finally, we show that $G_0W_0$@WOT-SRSH significantly reduces the sensitivity of computed band gaps to ambiguities in the underlying WOT-SRSH tuning procedure.

Near-Infrared Optical Response and Carrier Dynamics for High Photoconversion in Tellurene

Materials for applications in solar cells require a combination of features including an appropriate band gap and long relaxation times for photoexcited hot carriers. On the basis of ab initio many-body perturbation theory, including the spin–orbit interaction, we investigate the photocarrier generation and dynamics in α-tellurene. We show that photoexcited electrons are mainly generated in the near-infrared range, starting at 0.89 eV and forming excitons that are strongly bound, compared to its bulk counterpart, with a binding energy of 0.31 eV. We also explore the role of the electron–phonon interaction, finding that the electronic states in the first conduction band minimum couples weakly with phonons, yielding longer hot electron lifetimes (up to 70 fs) and mean free paths up to 37 nm. We also show that the extraction of hot holes may result in a challenging task as these carriers possess sub-3 nm mean free paths. We finally estimate that 1-nm-thick α-Te provides a short-circuit current density of 6.7 mA/cm2 and a maximum power conversion efficiency of 4.4%, which highlights its potential for efficient photovoltaic device development.

Relativistic Configuration-Interaction and Perturbation Theory Calculations of the Sn XV Emission Spectrum

Recently, there has been increased interest in developing advanced bright sources for lithography. Sn ions are particularly promising due to their bright emission spectrum in the required wavelength range. Cowan’s code has been used to model the emission; however, it has adjustable parameters, which limit its predictive power, and it has limited relativistic treatment. Here, we present calculations based on ab initio relativistic configuration-interaction many-body perturbation theory (CI-MBPT), with relativistic corrections included at the Dirac-Fock level and core-polarization effects with the second-order MBPT. As a proof of principle that the theory is generally applicable to other Sn ions with proper development, we focused on one ion where direct comparison with experimental observations is possible. The theory can also be used for ions of other elements to predict emissions for optimization of plasma-based bright sources.

Boosted Solar Light Absorbance in PdS2/PtS2 Vertical Heterostructures for Ultrathin Photovoltaic Devices.

Transition-metal dichalcogenides (TMDs) represent a class of materials whose archetypes, such as MoS2 and WS2, possess exceptional electronic and optical properties and have been massively exploited in optoelectronic applications. The layered structure allows for their exfoliation to two-dimensional samples with atomic thickness (≲ 1 nm), promising for ultrathin, ultralight devices. In this work, by means of state-of-the-art ab initio many-body perturbation theory techniques, we focus on single-layer PdS2 and PtS2 and propose a novel van der Waals heterostructure with outstanding light absorbance, reaching up to 50% in the visible spectrum and yielding a maximum short-circuit current of 7.2 mA/cm2 under solar irradiation. The computed excitonic landscape predicts a partial charge separation between the two layers and the momentum-forbidden lowest-energy state increases the carrier diffusion length. Our results show that the employment of vertical heterostructures with less conventional TMDs, such as PdS2/PtS2, can greatly boost light absorbance and favor the development of more efficient, atomic-thin photovoltaic devices.

Assessment of the Ab Initio Bethe-Salpeter Equation Approach for the Low-Lying Excitation Energies of Bacteriochlorophylls and Chlorophylls.

Bacteriochlorophyll and chlorophyll molecules are crucial building blocks of the photosynthetic apparatus in bacteria, algae, and plants. Embedded in transmembrane protein complexes, they are responsible for the primary processes of photosynthesis: excitation energy and charge transfer. Here, we use ab initio many-body perturbation theory within the GW approximation and Bethe–Salpeter equation (BSE) approach to calculate the electronic structure and optical excitations of bacteriochlorophylls a, b, c, d, and e and chlorophylls a and b. We systematically study the effects of the structure, basis set size, partial self-consistency in GW, and the underlying exchange–correlation approximation and compare our calculations with results from time-dependent density functional theory, multireference RASPT2, and experimental literature results. We find that optical excitations calculated with GW+BSE are in excellent agreement with experimental data, with an average deviation of less than 100 meV for the first three bright excitations of the entire family of (bacterio)chlorophylls. Contrary to state-of-the-art time-dependent density functional theory (TDDFT) with an optimally tuned range-separated hybrid functional, this accuracy is achieved in a parameter-free approach. Moreover, GW+BSE predicts the energy differences between the low-energy excitations correctly and eliminates spurious charge transfer states that TDDFT with (semi)local approximations is known to produce. Our study provides accurate reference results and highlights the potential of the GW+BSE approach for the simulation of larger pigment complexes.

Chemically Localized Resonant Excitons in Silver-Pnictogen Halide Double Perovskites.

Halide double perovskites with alternating silver and pnictogen cations are an emerging family of photoabsorber materials with robust stability and band gaps in the visible range. However, the nature of optical excitations in these systems is not yet well understood, limiting their utility. Here, we use ab initio many-body perturbation theory within the GW approximation and the Bethe–Salpeter equation approach to calculate the electronic structure and optical excitations of the double perovskite series Cs2AgBX6, with B = Bi3+, Sb3+ and X = Br–, Cl–. We find that these materials exhibit strongly localized resonant excitons with energies from 170 to 434 meV below the direct band gap. In contrast to lead-based perovskites, the Cs2AgBX6 excitons are computed to be non-hydrogenic with anisotropic effective masses and sensitive to local field effects, a consequence of their chemical heterogeneity. Our calculations demonstrate the limitations of the Wannier–Mott and Elliott models for this class of double perovskites and contribute to a detailed atomistic understanding of their light–matter interactions.

Spatially indirect excitons in black and blue phosphorene double layers

Monolayer black and blue phosphorenes possess electronic and optical properties that result in unique features when the two materials are stacked. We devise a low-strain van-der-Waals double layer and investigate its properties with ab initio many-body perturbation theory techniques. A type-II band alignment and optical absorption in the visible range are found. The study demonstrates that spatially indirect excitons with full charge separation can be obtained between two layers with the same elemental composition but different crystalline structure, proving the system interesting for further studies where dipolar excitons are important and for future opto-electronic applications.

Reproducibility in [formula omitted] calculations for solids

Ab initio many-body perturbation theory within the GW approximation is a Green’s function formalism widely used in the calculation of quasiparticle excitation energies of solids. In what has become an increasingly standard approach, Kohn–Sham eigenenergies, generated from a DFT calculation with a strategically-chosen exchange–correlation functional “starting point”, are used to construct G and W, and then perturbatively corrected by the resultant GW self-energy. In practice, there are several ways to construct the GW self-energy, and these can lead to variations in predicted quasiparticle energies. For example, for ZnO and TiO2, the GW fundamental gaps reported in the literature can vary by more than 1 eV depending on the GW code used. In this work, we calculate and analyze GW quasiparticle (QP) energies of these and other systems with three different GW codes: BerkeleyGW, Abinit and Yambo. Through a systematic analysis of the GW implementation of these three codes, we identify the primary origin of major discrepancies between codes reported in prior literature to be the different implementations the Coulomb divergence in the Fock exchange term and the frequency integration scheme of the GW self-energy. We then eliminate these discrepancies by using common numerical methods and algorithms, demonstrating that the same quasiparticle energies for a given material can be obtained with different codes, within numerical differences ascribable to the technical details of the underling implementations. This work will be important for users and developers in assessing the precision of future GW applications and methods.

Electro-optical properties of a pressure-induced g−SiC7 sheet from many-body perturbation theory

Alongside a vast number of two-dimensional (2D) materials, $g\text{\ensuremath{-}}{\mathrm{SiC}}_{7}$ siligraphene has already been introduced to the 2D nanomaterial family with extraordinary sunlight absorption. In this work, we exploit the concept of the in-plane biaxial strain-induced electro-optical engineering in siligraphene from ab initio many-body perturbation theory calculations (GW + Bethe-Salpeter equation). While the semiconductor nature of the system is robust for both tensile and compressive strains, the direct GW band gap of 1.35 eV is decreased (increased) linearly with tensile (compressive) strain. This is accompanied by a variation in the optical transitions. The tensile strain in $g\text{\ensuremath{-}}{\mathrm{SiC}}_{7}$ shifts the optical absorption peaks to the lower photon energies, the so-called red shift, whereas the compressive strain causes a shift to the higher frequencies, the so-called blue shift. Eventually, the exciton binding energy trend and the real-space exciton distribution for the bright bound state is studied with strain, resulting in a alteration of the spatial distribution radius of exciton wave functions from tensile to compressive. Our findings extend the logic applications of siligraphene in photovoltaic devices, especially in tailoring the power conversion efficiency of excitonic solar cells.

Real-space exciton distribution in strained-siligraphene g-SiC7

Siligraphene belonging to the family of two-dimensional (2D) materials has great potential in optoelectronics due to its considerable excitonic effects. In this study, the strain effects on the electronic structure and the real-space exciton wave functions of g-SiC7 are investigated using the first-principles calculations based on the ab initio many-body perturbation theory. Alongside the increase (decrease) of the bandgap with compressive (tensile) strain, our results show that the exciton in the siligraphene monolayer under in-plane biaxial compressive strains is much more localized than that in the case of tensile one, leading to the higher and lower exciton binding energies, respectively. Moreover, the π↦π and π↦σ exciton state transition emerges when applying the compressive and tensile strains, respectively. Overall, our study reveals that a desirable way to dissociate the electron-hole coupling and to reduce the electron-hole recombination process is applying “in-plane biaxial tensile strain,” making g-SiC7 an excellent potential functional 2D semiconductor in optoelectronics.

Electronic Excitations of Polythiophene within Many-Body Perturbation Theory with and without the Tamm-Dancoff Approximation.

Excited electronic states of small and large π-conjugated organic molecules can be described within ab initio many-body perturbation theory, notably by the GW approximation for the electron self-energy operator combined with the Bethe-Salpeter equation for correlated electron-hole excitations. In this context, the Tamm-Dancoff approximation is routinely employed to reduce the computational effort. It is known that the use of this approximation introduces errors of several 100 meV for small organic molecules but is negligible for extended systems. In this paper, we investigate how exactly the transition between these two regimes happens, by calculating the optical excitation energies of a series of polythiophene molecules of different sizes. We determine which parts of the electron-hole interaction are responsible for the deviation and show that the quantitative effects of the Tamm-Dancoff approximation depend sensitively on the size of the electronic system, in particular on the electronic conjugation length.