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Zr-based MXenes recently attracted attention because of its experimental preparation showing temperature stability, mechanical strength, and promising energy, sensoric, and electrochemistry applications. However, necessary theoretical predictions at a precise/predictive level are complicated due to essential excitonic features and strong electron correlation (i.e., a necessity to go beyond standard density functional theory, DFT). Contrary to the prevailing focus on oxygen-terminated MXenes and standard predictions of other Zr-based MXenes as conductors, based on the hybrid DFT and GW many-body perturbational theory, we were able to find seven different semiconductors (five of them for their equilibrium geometry and two others under slight tensile biaxial strain) in the case of two- and three-layered Z r 2 C T 2 and Z r 3 C 2 T 2 configurations with various terminations (T = O, F, S, Cl). We observed semiconductor-to-conductor transition induced by strain in the majority of such Zr-based MXenes at an experimentally achievable strain range. Furthermore, using the Bethe–Salpeter equation (BSE), we demonstrated that selected semiconducting Zr-based MXenes possess high optical absorption efficiency (20%–30%) in the visible light range, underscoring their potential in photonic applications. The high sensitivity of Zr-based MXenes to external conditions and functionalization combined with the thermal stability makes the materials promising for applications at operational temperatures in electronic and optical technologies. [ABSTRACT FROM AUTHOR]

The projector augmented wave (PAW) method of Blöchl linearly maps smooth pseudo wavefunctions to the highly oscillatory all-electron DFT orbitals. Compared to norm-conserving pseudopotentials (NCPP), PAW has the advantage of lower kinetic energy cutoffs and larger grid spacing at the cost of having to solve for non-orthogonal wavefunctions. We earlier developed orthogonal PAW (OPAW) to allow the use of PAW when orthogonal wavefunctions are required. In OPAW, the pseudo wavefunctions are transformed through the efficient application of powers of the PAW overlap operator with essentially no extra cost compared to NCPP methods. Previously, we applied OPAW to DFT. Here, we take the first step to make OPAW viable for post-DFT methods by implementing it in real-time time-dependent (TD) DFT. Using fourth-order Runge–Kutta for the time-propagation, we compare calculations of absorption spectra for various organic and biological molecules and show that very large grid spacings are sufficient, 0.6–0.7 bohr in OPAW-TDDFT rather than the 0.4–0.5 bohr used in traditional NCPP-TDDFT calculations. This reduces the memory and propagation costs by around a factor of 3. Our method would be directly applicable to any post-DFT methods that require time-dependent propagations such as the GW approximation and the Bethe–Salpeter equation. [ABSTRACT FROM AUTHOR]

Semiconducting MXenes are an intriguing two-dimensional (2D) material class with promising electronic and optoelectronic properties. Here, we focused on recently prepared Hf-based MXenes, namely, Hf3C2O2 and Hf2CO2. Using the first-principles calculation and excited state corrections, we proved their dynamical stability, reconciled their semiconducting behavior, and obtained fundamental gaps by using the many-body GW method (indirect 1.1 and 2.2 eV; direct 1.4 and 3.5 eV). Using the Bethe–Salpeter equation, we subsequently provided optical gaps (0.9 and 2.7 eV, respectively), exciton binding energies, absorption spectra, and other properties of excitons in both Hf-based MXenes. The indirect character of both 2D materials further allowed for a significant decrease of excitation energies by considering indirect excitons with exciton momentum along the Γ-M path in the Brillouin zone. The first bright excitons are strongly delocalized in real space while contributed by only a limited number of electron–hole pairs around the M point in the k-space from the valence and conduction band. A diverse range of excitonic states in Hf3C2O2 MXene lead to a 4% and 13% absorptance for the first and second peaks in the infrared region of absorption spectra, respectively. In contrast, a prominent 28% absorptance peak in the visible region appears in Hf2CO2 MXene. Results from radiative lifetime calculations indicate the promising potential of these materials in optoelectric devices requiring sustained and efficient exciton behavior. [ABSTRACT FROM AUTHOR]

We review the GPAW open-source Python package for electronic structure calculations. GPAW is based on the projector-augmented wave method and can solve the self-consistent density functional theory (DFT) equations using three different wave-function representations, namely real-space grids, plane waves, and numerical atomic orbitals. The three representations are complementary and mutually independent and can be connected by transformations via the real-space grid. This multi-basis feature renders GPAW highly versatile and unique among similar codes. By virtue of its modular structure, the GPAW code constitutes an ideal platform for the implementation of new features and methodologies. Moreover, it is well integrated with the Atomic Simulation Environment (ASE), providing a flexible and dynamic user interface. In addition to ground-state DFT calculations, GPAW supports many-body GW band structures, optical excitations from the Bethe–Salpeter Equation, variational calculations of excited states in molecules and solids via direct optimization, and real-time propagation of the Kohn–Sham equations within time-dependent DFT. A range of more advanced methods to describe magnetic excitations and non-collinear magnetism in solids are also now available. In addition, GPAW can calculate non-linear optical tensors of solids, charged crystal point defects, and much more. Recently, support for graphics processing unit (GPU) acceleration has been achieved with minor modifications to the GPAW code thanks to the CuPy library. We end the review with an outlook, describing some future plans for GPAW. [ABSTRACT FROM AUTHOR]

The properties of excitons, or correlated electron-hole pairs, are of paramount importance to optoelectronic applications of materials. A central component of exciton physics is the electron-hole interaction, which is commonly treated as screened solely by electrons within a material. However, nuclear motion can screen this Coulomb interaction as well, with several recent studies developing model approaches for approximating the phonon screening of excitonic properties. While these model approaches tend to improve agreement with experiment, they rely on several approximations that restrict their applicability to a wide range of materials, and thus far they have neglected the effect of finite temperatures. Here, we develop a fully first-principles, parameter-free approach to compute the temperature-dependent effects of phonon screening within the ab initio [Formula: see text]-Bethe-Salpeter equation framework. We recover previously proposed models of phonon screening as well-defined limits of our general framework, and discuss their validity by comparing them against our first-principles results. We develop an efficient computational workflow and apply it to a diverse set of semiconductors, specifically AlN, CdS, GaN, MgO, and [Formula: see text]. We demonstrate under different physical scenarios how excitons may be screened by multiple polar optical or acoustic phonons, how their binding energies can exhibit strong temperature dependence, and the ultrafast timescales on which they dissociate into free electron-hole pairs.

Spin-flip (SF) methods applied to excited-state approaches like the Bethe-Salpeter equation allow access to the excitation energies of open-shell systems, such as molecules and defects in solids. The eigenstates of these solutions, however, are generally not eigenstates of the spin operator Formula presented. Even for simple cases where the excitation vector is expected to be, for example, a triplet state, the value of ⟨Formula presented⟩ may be found to differ from 2.00; this difference is called ‘spin contamination’. The expectation values ⟨Formula presented⟩ must be computed for each excitation vector, to assist with the characterization of the particular excitation and to determine the amount of spin contamination of the state. Our aim is to provide for the first time in the SF methods literature a comprehensive resource on the derivation of the formulas for ⟨Formula presented⟩ as well as its computational implementation. After a brief discussion of the theory of the SF Bethe-Salpeter equation (BSE) and some examples further illustrating the need for calculating ⟨Formula presented⟩ , we present the derivation for the general equation for computing ⟨Formula presented⟩ with the eigenvectors from an SF-BSE calculation, how it is implemented in a Python script, and timing information on how this calculation scales with the size of the SF-BSE Hamiltonian.

A route to assess non-linear light–matter interactions from the increasingly popular GW-Bethe–Salpeter equation (GW-BSE) method is outlined. In the present work, the necessary analytic expressions within the static-screened exchange approximation of the BSE are derived. This enables a straightforward implementation of the computation of the first hyperpolarizability as well as two-photon absorption processes for molecular systems. Benchmark calculations on small molecular systems reveal that the GW-BSE method is intriguingly accurate for predicting both first hyperpolarizabilities and two-photon absorption strengths. Using state-of-the-art Kohn–Sham references as a starting point, the accuracy of the GW-BSE method rivals that of the coupled-cluster singles-and-doubles method, outperforming both second-order coupled-cluster and time-dependent density-functional theory. [ABSTRACT FROM AUTHOR]

Metal-halide perovskites are a structurally, chemically, and electronically diverse class of semiconductors with applications ranging from photovoltaics to radiation detectors and sensors. Understanding neutral electron–hole excitations (excitons) is key for predicting and improving the efficiency of energy-conversion processes in these materials. First-principles calculations have played an important role in this context, allowing for a detailed insight into the formation of excitons in many different types of perovskites. Such calculations have demonstrated that excitons in some perovskites significantly deviate from canonical models due to the chemical and structural heterogeneity of these materials. In this Perspective, I provide an overview of calculations of excitons in metal-halide perovskites using Green's function-based many-body perturbation theory in the GW + Bethe–Salpeter equation approach, the prevalent method for calculating excitons in extended solids. This approach readily considers anisotropic electronic structures and dielectric screening present in many perovskites and important effects, such as spin–orbit coupling. I will show that despite this progress, the complex and diverse electronic structure of these materials and its intricate coupling to pronounced and anharmonic structural dynamics pose challenges that are currently not fully addressed within the GW + Bethe–Salpeter equation approach. I hope that this Perspective serves as an inspiration for further exploring the rich landscape of excitons in metal-halide perovskites and other complex semiconductors and for method development addressing unresolved challenges in the field. [ABSTRACT FROM AUTHOR]

Based on density functional theory (DFT), the GW approximation and Bethe–Salpeter equation (BSE), we performed a theoretical calculation to study the electronic and optical properties of penta-graphene (PG) monolayers. Our findings reveal that PG behaves as a semiconductor with an indirect band gap of 2.27 eV at the DFT-GGA level. By incorporating the GW approximation based on many-body perturbation theory, we observed an increase in the band gap, resulting in a quasi-direct band gap of 4.53 eV. Furthermore, we employed the G0W0-RPA and G0W0-BSE approximations to compute the optical spectra of the monolayer in the absence and in the presence of electron–hole interaction, respectively. The results indicate that the inclusion of electron–hole interactions leads to a red-shift of the absorption spectrum towards lower energies compared to the spectrum obtained from the G0W0-RPA approximation. Notably, the optical absorption spectra are predominantly governed by the first bound exciton, characterized by a significant binding energy of 2.07 eV. Our results suggest that the PG monolayer, with its wider band gap and enhanced excitonic effects, is potentially a suitable candidate for the design and fabrication of optoelectronic components. [ABSTRACT FROM AUTHOR]

The performance of HfSSe/Arsenene van der Waals heterostructure in photocatalytic water splitting based on density functional theory (DFT) is investigated, in which the heterostructure is categorized into two configurations, S-As and Se-As, according to the distances of S and Se to the Arsenene layer. Calculations of the band structures, work functions, electron transfer, and band-edge position reveal that both the configurations are identified as direct Z-scheme heterojunction in photocatalysis. Moreover, the hydrogen evolution reaction (HER) occurs on the Arsenene surface, while the oxygen evolution reaction (OER) occurs on the HfSSe surface. After forming a monolayer HfSSe/Arsenene heterojunction, the carrier mobility of the system is increased. Furthermore, the optical properties of the system have been studied using the G 0 W 0 +BSE (Bethe-Salpeter equation) method, and the results show an increase in the absorption coefficient in both visible and ultraviolet regions. Additionally, the absorption coefficient of the heterostructure is significantly affected by conducting biaxial strains, thus further alters the reactivity of hydrogen evolution reaction and oxygen evolution reaction. • HfSSe can be combined with Arsenene to a stable HfSSe/Arsenene heterojunction. • Both S-As and Se-As heterojunctions are direct Z-scheme photocatalysts. • The heterojunctions has the appropriate overpotentials for the redox reactions. • Biaxial strain affects HER and OER reactivity. [ABSTRACT FROM AUTHOR]

A two-component contour deformation (CD) based GW method that employs frequency sampling to drastically reduce the computational effort when assessing quasiparticle states far away from the Fermi level is outlined. Compared to the canonical CD-GW method, computational scaling is reduced by an order of magnitude without sacrificing accuracy. This allows for an efficient calculation of core ionization energies. The improved computational efficiency is used to provide benchmarks for core ionized states, comparing the performance of 15 density functional approximations as Kohn–Sham starting points for GW calculations on a set of 65 core ionization energies of 32 small molecules. Contrary to valence states, GW calculations on core states prefer functionals with only a moderate amount of Hartree–Fock exchange. Moreover, modern ab initio local hybrid functionals are also shown to provide excellent generalized Kohn–Sham references for core GW calculations. Furthermore, the core–valence separated Bethe–Salpeter equation (CVS-BSE) is outlined. CVS-BSE is a convenient tool to probe core excited states. The latter is tested on a set of 40 core excitations of eight small inorganic molecules. Results from the CVS-BSE method for excitation energies and the corresponding absorption cross sections are found to be in excellent agreement with those of reference damped response BSE calculations. [ABSTRACT FROM AUTHOR]

In recent years, Green's function methods have garnered considerable interest due to their ability to target both charged and neutral excitations. Among them, the well-established GW approximation provides accurate ionization potentials and electron affinities and can be extended to neutral excitations using the Bethe–Salpeter equation (BSE) formalism. Here, we investigate the connections between various Green's function methods and evaluate their performance for charged and neutral excitations. Comparisons with other widely known second-order wave function methods are also reported. Additionally, we calculate the singlet-triplet gap of cycl[3,3,3]azine, a model molecular emitter for thermally activated delayed fluorescence, which has the particularity of having an inverted gap thanks to a substantial contribution from the double excitations. We demonstrate that, within the GW approximation, a second-order BSE kernel with dynamical correction is required to predict this distinctive characteristic. [ABSTRACT FROM AUTHOR]

We present an implementation of excited-state analytic gradients within the Bethe–Salpeter equation formalism using an adapted Lagrangian Z-vector approach with a cost independent of the number of perturbations. We focus on excited-state electronic dipole moments associated with the derivatives of the excited-state energy with respect to an electric field. In this framework, we assess the accuracy of neglecting the screened Coulomb potential derivatives, a common approximation in the Bethe–Salpeter community, as well as the impact of replacing the GW quasiparticle energy gradients by their Kohn–Sham analogs. The pros and cons of these approaches are benchmarked using both a set of small molecules for which very accurate reference data are available and the challenging case of increasingly extended push–pull oligomer chains. The resulting approximate Bethe–Salpeter analytic gradients are shown to compare well with the most accurate time-dependent density-functional theory (TD-DFT) data, curing in particular most of the pathological cases encountered with TD-DFT when a nonoptimal exchange–correlation functional is used. [ABSTRACT FROM AUTHOR]

We develop an improved stochastic formalism for the Bethe–Salpeter equation (BSE), based on an exact separation of the effective-interaction W into two parts, W = (W − vW) + vW, where the latter is formally any translationally invariant interaction, vW(r − r′). When optimizing the fit of the exchange kernel vW to W, using a stochastic sampling W, the difference W − vW becomes quite small. Then, in the main BSE routine, this small difference is stochastically sampled. The number of stochastic samples needed for an accurate spectrum is then largely independent of system size. While the method is formally cubic in scaling, the scaling prefactor is small due to the constant number of stochastic orbitals needed for sampling W. [ABSTRACT FROM AUTHOR]

Lead halide perovskites are structurally not stable due to their ionic bonds. Using sulfur agents in the crystal growth improves the stability and performance of the photovoltaic and light‐emitting devices. In this theoretical work, we use a small toy S‐radical in place of A cation in the bulk of lead iodide perovskite, and highlight the significance of the Pb−S covalent‐double‐bond formation for: the charge redistribution on the neighboring bonds that also turn to be covalent, phase transformation to a stable non‐perovskite structure, and superior optoelectronic properties. The chemical analysis was performed with the Quantum Theory of Atoms In Molecules (QTAIM) and Non‐Covalent Interactions (NCI) index. Excitonic properties were obtained from the solution of ab initio Bethe–Salpeter equation. Presence of the spin‐orbit coupling triggers an interplay between the Frenkel and charge‐transfer multiexcitons, switching between the photovoltaic and laser applications. Multiexcitons obey the exciton‐fission preconditions. [ABSTRACT FROM AUTHOR]

Systematic investigation of energy levels of Λ hypernuclei enables physicists to determine a considerable number of details about the inner structure of these particles as well as the interaction dynamics of Λ nucleon. Of importance is to develop the theoretical tools to study spectroscopy of hypernuclei. In this regard, our aim is to specify the mass spectra and the binding energies of Λ hypernuclei in their ground and excited states. Then, we first present an analytical solution for the Bethe–Salpeter equation of single Λ hypernuclei taking the Woods–Saxon interaction potential. Through a good approximation, we present an analytical expression for the binding energies in the ground and excited states, i.e., 1p, 1d, 1f and 1g shells. We also give numerical results for Λ binding energies of light and heavy hypernuclei. Our numerical analysis is compared with experimental data so that good consistencies between both results confirm the approach used to analysis the Λ–nucleon interaction. [ABSTRACT FROM AUTHOR]

Correlated classical and quantum many‐particle systems out of equilibrium are of high interest in many fields, including dense plasmas, correlated solids, and ultracold atoms. Accurate theoretical description of these systems is challenging both, conceptionally and with respect to computational resources. While for classical systems, in principle, exact simulations are possible via molecular dynamics, this is not the case for quantum systems. Alternatively, one can use many‐particle approaches such as hydrodynamics, kinetic theory, or nonequilibrium Green functions (NEGF). However, NEGF exhibit a very unfavorable cubic scaling of the CPU time with the number of time steps. An alternative is the G1–G2 scheme [N. Schlünzen et al., Phys. Rev. Lett. 124, 076601 (2020)] which allows for NEGF simulations with time linear scaling, however, at the cost of large memory consumption. The reason is the need to store the two‐particle correlation function. This problem can be overcome for a number of approximations by reformulating the kinetic equations in terms of fluctuations – an approach that was developed, for classical systems, by Yu.L. Klimontovich [JETP 33, 982 (1957)]. Here, we present an overview of his ideas and extend them to quantum systems. In particular, we demonstrate that this quantum fluctuations approach can reproduce the nonequilibrium GW approximation [E. Schroedter et al., Cond. Matt. Phys. 25, 23401 (2022)] promising high accuracy at low computational cost which arises from an effective semiclassical stochastic sampling procedure. We also demonstrate how to extend the approach to the two‐time exchange‐correlation functions and the density response properties. [E. Schroedter et al., Phys. Rev. B 108, 205109 (2023)]. The results are equivalent to the Bethe–Salpeter equation for the two‐time exchange‐correlation function when the generalized Kadanoff‐Baym ansatz with Hartree‐Fock propagators is applied [E. Schroedter and M. Bonitz, phys. stat. sol. (b) 2024, 2300564]. [ABSTRACT FROM AUTHOR]

Sc2C(OH)2 is a prototypical non-magnetic member of MXenes, a promising transition-metal-based 2D material family, with a direct bandgap. We provide here a benchmark of its fundamental gap Δ obtained from many-body GW and fixed-node diffusion Monte Carlo methods. Both approaches independently arrive at a similar value of Δ ∼ 1.3 eV, suggesting the validity of both methods. Such a bandgap makes Sc2C(OH)2 a 2D semiconductor suitable for optoelectronic applications. The absorbance spectra and the first exciton binding energy (0.63 eV), based on the Bethe–Salpeter equation, are presented as well. The reported results may serve to delineate experimental uncertainties and enable selection of reasonable approximations such as density functional theory functionals, for use in modeling of related MXenes. [ABSTRACT FROM AUTHOR]

Here, we build on the works of Scuseria et al. [J. Chem. Phys. 129, 231101 (2008)] and Berkelbach [J. Chem. Phys. 149, 041103 (2018)] to show connections between the Bethe–Salpeter equation (BSE) formalism combined with the GW approximation from many-body perturbation theory and coupled-cluster (CC) theory at the ground- and excited-state levels. In particular, we show how to recast the GW and Bethe–Salpeter equations as non-linear CC-like equations. Similitudes between BSE@GW and the similarity-transformed equation-of-motion CC method are also put forward. The present work allows us to easily transfer key developments and the general knowledge gathered in CC theory to many-body perturbation theory. In particular, it may provide a path for the computation of ground- and excited-state properties (such as nuclear gradients) within the GW and BSE frameworks. [ABSTRACT FROM AUTHOR]

Abstract In this paper, we investigate the optical, electronic, vibrational, and excitonic properties of four two-dimensional $$\beta$$ β -pnictogen materials—nitrogenene, phosphorene, arsenene, and antimonene—via density functional theory calculations and the Bethe–Salpeter equation. These materials possess indirect gaps with significant exciton binding energies, demonstrating isotropic behavior under circular light polarization and anisotropic behavior under linear polarization by absorbing light within the visible solar spectrum (except for nitrogenene). Furthermore, we observed that Raman frequencies red-shift in heavier pnictogen atoms aligning with experimental observations; simultaneously, quasi-particle effects notably influence the linear optical response intensively. These monolayers’ excitonic effects lead to optical band gaps optimized for solar energy harvesting, positioning them as promising candidates for advanced optoelectronic device applications.

We present a benchmark study of excited state potential energy surfaces (PES) using the many-body Green's function GW and Bethe–Salpeter equation (BSE) formalisms, coupled cluster methods, as well as Time-Dependent Density Functional Theory (TD-DFT). More specifically, we investigate the evolution of the two lowest excited states of 4-(dimethylamino)benzonitrile (DMABN) upon the twisting of the amino group, a paradigmatic system for dual fluorescence and excited-state benchmarks. Our results demonstrate that the BSE/GW approach is able to reproduce the correct topology of excited state PES upon geometry changes in both gas and condensed phases. The vertical transition energies predicted by BSE/GW are indeed in good agreement with coupled cluster values, including triples. The BSE approach ability to include both linear response and state-specific solvent corrections further enables it to accurately describe the solvatochromism of both excited states during the twisting of DMABN. This contribution stands as one of the first proof-of-concept that BSE/GW PES should be accurate in cases for which TD-DFT struggles, including the central case of systems embedded in a dielectric environment. [ABSTRACT FROM AUTHOR]

The structural, electronic, and optical properties of CdSe/CdS core–shell colloidal quantum dot molecules, a new class of coupled quantum dot dimers, are explored using atomistic approaches. Unlike the case of dimers grown by molecular beam epitaxy, simulated strain profile maps of free-standing colloidal dimers show negligible additional strain resulting from the attachment. The electronic properties of the relaxed dimers are described within a semiempirical pseudopotential model combined with the Bethe–Salpeter equation within the static screening approximation to account for electron–hole correlations. The interplay of strain, hybridization (tunneling splitting), quantum confinement, and electron–hole binding energies on the optical properties is analyzed and discussed. The effects of the dimensions of the neck connecting the two quantum dot building blocks, as well as the shell thickness, are studied. [ABSTRACT FROM AUTHOR]

Photocatalytic materials are of great scientific interest due to their potential applications in sustainable energy sources. Band gap and optical absorption of the materials are two core characteristics for photocatalysis that eventually depend on electronic structure. In order to accurately compute (predict) the electronic‐scale properties of a crystalline solid using first principles calculations, which might be costly to measure experimentally, large‐scale atomic level calculation frameworks have been made possible through the use of density functional theory (DFT). We have used DFT with many body perturbation theory (MBPT) by solving the bethe‐salpeter equation (BSE) to priorly predict the properties of bulk tin sulfide (SnS) as it meets the necessary requirements for photocatalytic applications. We fixed the DFT band gap underestimation by including the Hubbard parameter (U) and used projector augmented wave pseudo‐potentials with generalized‐gradient approximation (GGA) to calculate the electronic and optical properties of SnS. Optical properties were computed using independent particle approximation (IPA) and BSE with DFT+U wave functions. Our theoretical results align with experimental data for this material, demonstrating the potential for further research in validating experimental results with theoretical approximations and empirical relations. [ABSTRACT FROM AUTHOR]

Photocatalytic materials are of great scientific interest due to their potential applications in sustainable energy sources. Band gap and optical absorption of the materials are two core characteristics for photocatalysis that eventually depend on electronic structure. In order to accurately compute (predict) the electronic‐scale properties of a crystalline solid using first principles calculations, which might be costly to measure experimentally, large‐scale atomic level calculation frameworks have been made possible through the use of density functional theory (DFT). We have used DFT with many body perturbation theory (MBPT) by solving the bethe‐salpeter equation (BSE) to priorly predict the properties of bulk tin sulfide (SnS) as it meets the necessary requirements for photocatalytic applications. We fixed the DFT band gap underestimation by including the Hubbard parameter (U) and used projector augmented wave pseudo‐potentials with generalized‐gradient approximation (GGA) to calculate the electronic and optical properties of SnS. Optical properties were computed using independent particle approximation (IPA) and BSE with DFT+U wave functions. Our theoretical results align with experimental data for this material, demonstrating the potential for further research in validating experimental results with theoretical approximations and empirical relations. [ABSTRACT FROM AUTHOR]

The many‐body GW combined with the Bethe–Salpeter equation (BSE) method including the spin‐orbit coupling (SOC) effect has been adopted to revisit the band structure and optical absorption spectra evolution of single‐layer, double‐layer, three‐layer, and bulk InSe. The many‐body effect is found to play an important role in both the band structure and the optical properties of InSe structures. Not only the band gap but also the energy dispersion is influenced by the electron–electron many‐body interaction. Electron–hole interaction strongly affects the optical properties of InSe structures, especially the single‐layer InSe. Compared with previous reports, the calculations show that, including SOC, two bound excitonic peaks have emerged for monolayer InSe, with the strong bound exciton being s‐state‐like, while the other p‐state‐like. BSE also predicts abundance of bounded "dark" excitons exists for monolayer InSe, indicating that monolayer InSe is a proper platform for studying excitons. Although the spin‐orbit interaction influence on the highest valence band and the lowest conducted band seems trivial, its effect on the optical properties of InSe is remarkable. [ABSTRACT FROM AUTHOR]

Positron bound state properties in hydrogen cyanide are studied via many-body theory calculations that account for strong positron-electron correlations including positron-induced polarization, screening of the electron–positron Coulomb interaction, virtual-positronium formation and positron–hole repulsion. Specifically, the Dyson equation is solved using a Gaussian basis, with the positron self-energy in the field of the molecule calculated using the Bethe–Salpeter equations for the two-particle and particle–hole propagators. The present results suggest near cancellation of screening corrections to the bare polarization, and the non-negligible role of the positron–hole interaction. There are no existing measurements to compare to for HCN. Previous configuration interaction (CI) and fixed-node diffusion Monte Carlo (FN-DMC) calculations give positron binding energies in the range 35–44 meV, most of which used a single even-tempered basis centred near the nitrogen atom. Using a similar single-centre positron basis we calculate a positron binding energy of 41 meV, in good agreement. However, we find that including additional basis centres gives an improved description of the positron wave function near the nuclei, and results in a converged binding energy in the range 63–73 meV (depending on geometry and approximation to the positron–molecule correlation potential used). [ABSTRACT FROM AUTHOR]

Layered halide perovskites are solution‐processed natural heterostructures where quantum and dielectric confinement down to the nanoscale strongly influence the optical properties, leading to stabilization of bound excitons. Detailed understanding of the exciton properties is crucial to boost the exploitation of these materials in energy conversion and light emission applications, with on‐going debate related to the energy order of the four components of the most stable exciton. To provide theoretical feedback and solve among contrasting literature reports, this work performs ab initio solution of the Bethe–Salpeter equation (BSE) for symmetrized reference Cs2PbX4 (X = I and Br) models, with detailed interpretation of the spectroscopic observables based on group‐theory analysis. Simulations predict the following Edark < Ein‐plane < Eout‐of‐plane fine‐structure assignment, consistent with recent magneto‐absorption experiments and obtain similar increase in dark/bright splitting when going from lead‐iodide to a lead‐bromide composition as found experimentally. The authors further suggest that polar distortions may lead to stabilization of the in‐plane component and end‐up in a bright lowest exciton component, discuss exciton landscape over a broad energy range and clarify the exciton spin‐character, when large spin‐orbit coupling is in play, to rationalize the potential of halide perovskites as triplet sensitizers in combination with organic dyes. [ABSTRACT FROM AUTHOR]

2D Janus monolayers and van der Waals heterostructures (vdWHs) exhibit fascinating physical properties because of the destruction of symmetry. The interface‐dependent electronic and optical properties of vdWHs constructed by Janus Ga2STe and Al2STe are explored. The results reveal that all interfaces vdWHs exhibit staggered (type‐II) band alignment. Specifically, the S/Te and Te/Te interfaces vdWHs are indirect bandgap semiconductors, while the S/S and Te/S interfaces vdWHs are direct bandgap semiconductors. The staggered band alignment promotes the electron transfer between the donor and acceptor in vdWHs, and the power conversion efficiency (PCE) of the Te/Te interface vdWH is as high as 25.34%. Furthermore, both S/Te and Te/Te interfaces vdWHs can provide suitable photocatalytic performance for water splitting under pristine conditions. By applying biaxial strain, S/S and Te/S interfaces vdWHs can be used as a photocatalyst. Under the compressive strain of 1%, the PCE of Te/Te reaches 28.68%. Based on the G0W0 + Bethe–Salpeter equation, different interfaces vdWHs exhibit different landscapes of intralayer exciting or interlayer exciting. The revealed type‐II band alignment, strong optical absorption, and superior PCE of the Al2STe/Ga2STe vdWHs imply that these new proposed materials have broad application prospects in optoelectronic devices such as excitonic solar cells. [ABSTRACT FROM AUTHOR]

Tailoring the electronic, optical, and transport properties of low-dimensional semiconductor materials is essential to improve the light-conversion efficiency of thin-film solar cell materials. Here, using first-principles calculations and non-equilibrium Green functions, we investigate the enhancement of optoelectronic and transport properties of armchair graphene nanoribbons (AGNRs) upon adsorption of cadmium selenide clusters. Upon adsorption of a CdSe diatomic molecule on an AGNR, the most energetically favorable configuration is the cadmium end sitting on top of a carbon atom. The corresponding electronic bandgap reduces ∼5 times with respect to that of the pristine system, thanks to the formation of a polaron state formed by the p-orbital of the selenide atom. Upon adsorption of CdSe cyclohexane molecules, the bandgap of this system slightly shrinks by 0.121 eV with respect to the pristine system. The charge accumulation induced by these clusters significantly enhances the absorption coefficient of the adsorbed systems, resulting in a red shift of the optical spectra toward the infrared region. More interestingly, by solving the Bethe–Salpeter equations with the Tamm–Dancoff approximation, we provide a direct link between the first-principles optical prediction and experimental observations. In addition, the electron transfer from these molecules to the hosted systems increases the transmission spectra in the vicinity of the Fermi level, leading to a remarkable electronic current passing through these scattering regions. These results highlight the role of cadmium selenide clusters in enhancing the light-to-energy conversion efficiency of next-generation solar cell devices. [ABSTRACT FROM AUTHOR]

The ab initio GW plus Bethe–Salpeter equation (GW-BSE, where G is the one particle Green's function and W is the screened Coulomb interaction) approach has emerged as a leading method for predicting excitations in both solids and molecules with a predictive power contingent upon several factors. Among these factors are the (1) generalized Kohn–Sham eigensystem used to construct the GW self-energy and to solve the BSE and (2) the efficacy and suitability of the Tamm–Dancoff approximation. Here, we present a detailed benchmark study of low-lying singlet excitations from a generalized Kohn–Sham (gKS) starting point based on an optimally tuned range-separated hybrid (OTRSH) functional. We show that the use of this gKS starting point with one-shot G0W0 and G0W0-BSE leads to the lowest mean absolute errors (MAEs) and mean signed errors (MSEs), with respect to high-accuracy reference values, demonstrated in the literature thus far for the ionization potentials of the GW100 benchmark set and for low-lying neutral excitations of Thiel's set molecules in the gas phase, without the need for self-consistency. The MSEs and MAEs of one-shot G0W0-BSE@OTRSH excitation energies are comparable to or lower than those obtained with other functional starting points after self-consistency. Additionally, we compare these results with linear-response time-dependent density functional theory (TDDFT) calculations and find GW-BSE to be superior to TDDFT when calculations are based on the same exchange-correlation functional. This work demonstrates tuned range-separated hybrids used in combination with GW and GW-BSE can greatly suppress starting point dependence for molecules, leading to accuracy similar to that for higher-order wavefunction-based theories for molecules without the need for costlier iterations to self-consistency. [ABSTRACT FROM AUTHOR]

We present a highly efficient method for the extraction of optical properties of very large molecules via the Bethe–Salpeter equation. The crutch of this approach is the calculation of the action of the effective Coulombic interaction, W, through a stochastic time-dependent Hartree propagation, which uses only ten stochastic orbitals rather than propagating the full sea of occupied states. This leads to a scaling that is at most cubic in system size with trivial parallelization of the calculation. We apply this new method to calculate the spectra and electronic density of the dominant excitons of a carbon-nanohoop bound fullerene system with 520 electrons using less than 4000 core hours. [ABSTRACT FROM AUTHOR]

While the well-established GW approximation corresponds to a resummation of the direct ring diagrams and is particularly well suited for weakly correlated systems, the T-matrix approximation does sum ladder diagrams up to infinity and is supposedly more appropriate in the presence of strong correlation. Here, we derive and implement, for the first time, the static and dynamic Bethe–Salpeter equations when one considers T-matrix quasiparticle energies and a T-matrix-based kernel. The performance of the static scheme and its perturbative dynamical correction are assessed by computing the neutral excited states of molecular systems. A comparison with more conventional schemes as well as other wave function methods is also reported. Our results suggest that the T-matrix-based formalism performs best in few-electron systems where the electron density remains low. [ABSTRACT FROM AUTHOR]

We applied localized orbital scaling correction (LOSC) in Bethe–Salpeter equation (BSE) to predict accurate excitation energies for molecules. LOSC systematically eliminates the delocalization error in the density functional approximation and is capable of approximating quasiparticle (QP) energies with accuracy similar to or better than GW Green's function approach and with much less computational cost. The QP energies from LOSC, instead of commonly used G0W0 and evGW, are directly used in BSE. We show that the BSE/LOSC approach greatly outperforms the commonly used BSE/G0W0 approach for predicting excitations with different characters. For the calculations of Truhlar–Gagliardi test set containing valence, charge transfer, and Rydberg excitations, BSE/LOSC with the Tamm–Dancoff approximation provides a comparable accuracy to time-dependent density functional theory (TDDFT) and BSE/evGW. For the calculations of Stein CT test set and Rydberg excitations of atoms, BSE/LOSC considerably outperforms both BSE/G0W0 and TDDFT approaches with a reduced starting point dependence. BSE/LOSC is, thus, a promising and efficient approach to calculate excitation energies for molecular systems. [ABSTRACT FROM AUTHOR]

The Bethe–Salpeter equation (BSE) that results from the GW approximation to the self-energy is a frequency-dependent (nonlinear) eigenvalue problem due to the dynamically screened Coulomb interaction between electrons and holes. The computational time required for a numerically exact treatment of this frequency dependence is O(N6), where N is the system size. To avoid the common static screening approximation, we show that the full-frequency dynamical BSE can be exactly reformulated as a frequency-independent eigenvalue problem in an expanded space of single and double excitations. When combined with an iterative eigensolver and the density fitting approximation to the electron repulsion integrals, this reformulation yields a dynamical BSE algorithm whose computational time is O(N5), which we verify numerically. Furthermore, the reformulation provides direct access to excited states with dominant double excitation character, which are completely absent in the spectrum of the statically screened BSE. We study the 21Ag state of butadiene, hexatriene, and octatetraene and find that GW/BSE overestimates the excitation energy by about 1.5–2 eV and significantly underestimates the double excitation character. [ABSTRACT FROM AUTHOR]

Halide perovskites are widely used as components of electronic and optoelectronic devices such as solar cells, light-emitting diodes (LEDs), optically pumped lasers, field-effect transistors, photodetectors, and γ -detectors. Despite this wide range of applications, the construction of an electrically pumped perovskite laser remains challenging. In this paper, we numerically justify that mixing two perovskite compounds with different halide elements can lead to optical properties suitable for electrical pumping. As a reference, the chosen model material was CsPbBr 3 , whose performance as a part of lasers has been widely recognised, with some Br atoms substituted by I at specific sites. In particular, a strong enhancement of the low-energy absorption peaks has been obtained using the ab initio Bethe–Salpeter equation. Based on these results, we propose specific architectures of ordered doping that could be realised by epitaxial growth. Efficient light emission from the bottom of the conduction band is expected. [ABSTRACT FROM AUTHOR]

We study the possibly-existing molecular pentaquark states with open charm and bottom flavors, i.e., the states with the quark contents c b ¯ q q q and b c ¯ q q q ( q = u , d , s ). We investigate the meson-baryon interactions through the coupled-channel unitary approach within the local hidden-gauge formalism, and extract the poles by solving the Bethe-Salpeter equation in coupled channels. These poles qualify as molecular pentaquark states, which are dynamically generated from the meson-baryon interactions through the exchange of vector mesons. Our results suggest the existence of the Σ c (∗) B (∗) and Σ b (∗) D ¯ (∗) molecular states with isospin I = 1 / 2 , the Ξ c (′ , ∗) B (∗) and Ξ b (′ , ∗) D ¯ (∗) molecular states with isospin I = 0 and I = 1 , as well as the Ω c (∗) B (∗) and Ω b (∗) D ¯ (∗) molecular states with isospin I = 1 / 2 . [ABSTRACT FROM AUTHOR]

The Bethe–Salpeter equation for system of two oppositely charged particles not only reproduces the Coulomb spectrum, but, for enough large coupling constant C > π 4 , predicts additional levels not predicted by the Schrödinger equation. These relativistic states (called abnormal), in contrast to the normal ones, are dominated, for more than 90–99%, by Fock states involving the exchange particles—the photons, whereas contribution of two massive charged particles themselves is rather small (1–10%). Since the carrier of a large (positive) charge is a heavy ion, and the negative charge is provided by electron, the masses of two constituents are very different. It is shown that in a system with so different masses the abnormal states still exist. Moreover, the effect of unequal masses is attractive. The balance between photons and charged constituents is weakly sensitive to the mass ratio, so the photons still predominate. [ABSTRACT FROM AUTHOR]

Organic semiconductors based on conjugated donor-acceptor (D–A) polymers are a unique platform for electronic, spintronic, and energy-harvesting devices. Understanding the electronic structure of D–A polymers with a small band gap is essential for developing next-generation technologies. Here, we investigate the electronic structure and optical spectra of cyclopentadithiophene-based closed/open-shell D–A polymers using density functional theory and the Bethe–Salpeter equation based on G 0 W 0 approximation. We explored the role of different acceptor units and chemical substitutions on the structural changes and, more importantly, electronic, optical, and dielectric behavior. We found that the computed first exciton peak of the polymers agreed well with the available experimentally measured optical gap. Furthermore, D–A polymers with open-shell character display higher dielectric constant than the closed-shell polymers. We show that the exceptional performance of polycyclopentadithiophene-thiophenylthiadiazoloquinoxaline (PCPDT-TTQ) as a scalable n-type material for Faradaic supercapacitors can be partly ascribed to its elevated dielectric constant. Consequently, these D–A polymers, characterized by their high dielectric constants, exhibit significant potential for various applications, including energy storage, organic electronics, and the production of dielectric films. [ABSTRACT FROM AUTHOR]

We study the production of ground and excited axial charmonia in processes, e - e + → h c (n P) + η c (n ′ S) , and e - e + → χ c 1 (n P) + h c (n ′ P) for n , n ′ = 1 , 2 , through leading order tree-level diagrams ∼ O (α em α s) , which proceed through exchange of a virtual photon and an internal gluon line connecting two quark lines in the triangle quark loop part of the diagram at center of mass energy, s = 10.6 GeV . We employ the framework of 4 × 4 Bethe–Salpeter equation, and calculate their cross sections. These studies might be of interest for future experiments at B-factories, since h c , η c , and χ c 1 , h c production might provide opportunities for observing h c with higher statistics in future. [ABSTRACT FROM AUTHOR]

The applicability of the effective models to the description of baryons and the behaviour of ratios of strange baryons to pions is discussed. In the framework of the EPNJL model, the Bethe–Salpeter equation is used to find masses of baryons, which are considered to be in a diquark-quark state. Baryon melting is discussed at a finite chemical potential, and a flavor dependence of the hadronic deconfinement temperature is pointed out. It is shown that the description of the diquark-quark state at finite chemical potential is limited due to the occurrence of Bose condensate. This effect is strongly manifested in the description of light diquarks and baryons. Both the Λ 0 / π + and Ξ − / π + ratios show a sharp behaviour as functions of the T / μ B variable, where T and μ B are calculated along the melting lines. [ABSTRACT FROM AUTHOR]

One-particle Green's function methods can model molecular and solid spectra at zero or non-zero temperatures. One-particle Green's functions directly provide electronic energies and one-particle properties, such as dipole moment. However, the evaluation of two-particle properties, such as ⟨S2⟩ and ⟨N2⟩, can be challenging because they require a solution of the computationally expensive Bethe–Salpeter equation to find two-particle Green's functions. We demonstrate that the solution of the Bethe–Salpeter equation can be completely avoided. Applying the thermodynamic Hellmann–Feynman theorem to self-consistent one-particle Green's function methods, we derive expressions for two-particle density matrices in a general case and provide explicit expressions for GF2 and GW methods. Such density matrices can be decomposed into an antisymmetrized product of correlated one-electron density matrices and the two-particle electronic cumulant of the density matrix. Cumulant expressions reveal a deviation from ensemble representability for GW, explaining its known deficiencies. We analyze the temperature dependence of ⟨S2⟩ and ⟨N2⟩ for a set of small closed-shell systems. Interestingly, both GF2 and GW show a non-zero spin contamination and a non-zero fluctuation of the number of particles for closed-shell systems at the zero-temperature limit. [ABSTRACT FROM AUTHOR]

The optical and electronic properties of α-SiTe, β-SiTe, and RX-SiTe2 are investigated. A detailed analysis of electronic properties is done using standard density functional theory (DFT) and hybrid functional methods. The static dielectric properties are investigated using the density functional perturbation theory method. The optical properties are studied under three different methods: standard DFT, many-body Green's functions, and the Bethe–Salpeter equation. Our calculations show that the SiTe compounds possess extremely high static dielectric constants in their bulk forms [ε0(⊥) = 68.58 and ε0(‖) = 127.29 for α-SiTe, and ε0(⊥) = 76.23 and ε0(‖) = 74.61 for β-SiTe]. The frequency-dependent dielectric functions Im(ε) have very large values (>100) in the optical regime, which are among the highest of layered materials, suggesting them as excellent light absorbents in the corresponding frequencies. α-SiTe exhibits a high degree of optical anisotropy as compared to the other two compounds, consistent with their structural configurations. A strong interlayer excitonic effect is observed in bulk RX-SiTe2. In addition, an analysis of Raman intensity is also performed. [ABSTRACT FROM AUTHOR]

The momentum-forbidden dark excitons can have a pivotal role in quantum information processing, Bose-Einstein condensation, and light-energy harvesting. Anatase TiO2 with an indirect band gap is a prototypical platform to study bright to momentum-forbidden dark exciton transition. Here, we examine, by GW plus the real-time Bethe-Salpeter equation combined with the nonadiabatic molecular dynamics (GW + rtBSE-NAMD), the many-body transition that occurs within 100 fs from the optically excited bright to the strongly bound momentum-forbidden dark excitons in anatase TiO2. Comparing with the single-particle picture in which the exciton transition is considered to occur through electron-phonon scattering, within the GW + rtBSE-NAMD framework, the many-body electron-hole Coulomb interaction activates additional exciton relaxation channels to notably accelerate the exciton transition in competition with other radiative and nonradiative processes. The existence of dark excitons and ultrafast bright-dark exciton transitions sheds insights into applications of anatase TiO2 in optoelectronic devices and light-energy harvesting as well as the formation process of dark excitons in semiconductors. [ABSTRACT FROM AUTHOR]

The momentum-forbidden dark excitons can have a pivotal role in quantum information processing, Bose-Einstein condensation, and light-energy harvesting. Anatase TiO2 with an indirect band gap is a prototypical platform to study bright to momentum-forbidden dark exciton transition. Here, we examine, by GW plus the real-time Bethe-Salpeter equation combined with the nonadiabatic molecular dynamics (GW + rtBSE-NAMD), the many-body transition that occurs within 100 fs from the optically excited bright to the strongly bound momentum-forbidden dark excitons in anatase TiO2. Comparing with the single-particle picture in which the exciton transition is considered to occur through electron-phonon scattering, within the GW + rtBSE-NAMD framework, the many-body electron-hole Coulomb interaction activates additional exciton relaxation channels to notably accelerate the exciton transition in competition with other radiative and nonradiative processes. The existence of dark excitons and ultrafast bright-dark exciton transitions sheds insights into applications of anatase TiO2 in optoelectronic devices and light-energy harvesting as well as the formation process of dark excitons in semiconductors. [ABSTRACT FROM AUTHOR]

We have studied the dissociation of particle-antiparticle confined systems through a complex potential, which comes from adjusting and correcting both the perturbative and nonperturbative terms at finite temperatures. The real component of the confining nonperturbative potential makes the bound state stronger; in contrast, the absolute value of the imaginary component contributes more significantly to the thermal width at higher temperatures. The results are presented using the relativistic Bethe-Salpeter equation for the real and imaginary parts of the given potential within the framework of the asymptotic pattern and characteristics of the real and imaginarytime Green's functions of the bound state as charged particles that couple to a gauge field in any external field. The relativistic behavior of interaction within the Sturmian representation for two intertwined spaces was extracted based on the mathematical quantum field theory technique in the perturbative calculation of the quantum field theory. The expectation value of the vacuum of field operators is defined as a sum of operator product expansion methods. The results are applied to predict the masses of the charmonium confined state and study the heat dynamics and attributes of the system. The expectation values agree with the experimental and theoretical data found within scholarly works and among academic researchers. [ABSTRACT FROM AUTHOR]

In this paper, we carried out a critical investigation of the strong fluctuation theory using a quantum field theoretic approach [Tatarskii VI. The effects of the turbulent atmosphere on wave propagation. Jerusalem: IPST; 1971]. We employed the Dyson and Bethe-Salpeter equations to derive the radiative transfer equation (RTE) for the Green's function of the radiant intensity. We proceeded to obtain estimates of the domain of validity of the RTE. The results thus obtained satisfy both the optical theorem for waves in random media and energy conservation. We also derived the RTE for our problem by employing a recently developed scale-separated asymptotic theory [Bal G., Komorowski T, Ryzhik L. Kinetic limits of waves in random media. Kinet Relat Models. 2010;3:529–644]. Although the RTE obtained by the two approaches are identical, we explain that the applicability regimes, and hence validity conditions are different. [ABSTRACT FROM AUTHOR]

We study the properties of pseudoscalar mesons, pion, kaon, η and η ′ , and compute the γ ∗ γ → π 0 , η , η ′ transition form factor in the framework of the Schwinger–Dyson equations and Bethe–Salpeter equations, using a momentum independent contact interaction. The contact interaction is capable to describe the observable properties, but produces a transition form factor whose evolution for large Q 2 disagrees with experiment and perturbative QCD. Invited contribution to a Special Issue of Few Body Systems: "Emergence and Structure of Baryons—Selected Contributions from the International Conference Baryons 2022" [ABSTRACT FROM AUTHOR]