Model Of Electronic Structure Research Articles

Theoretical study of the temperature dependence of Auger-Meitner recombination in (Al,Ga)N quantum wells.

Non-radiative Auger-Meitner recombination processes in III-nitride based optoelectronic devices operating in the visible spectral range have received significant attention in recent years as they can present a major contribution to the efficiency drop at high temperatures and carrier densities. However, insight into these recombination processes is sparse for III-N devices operating in the ultraviolet wavelength window. In this work we target the temperature dependence of the Auger-Meitner recombination rate in (Al,Ga)N/AlN quantum wells by means of an atomistic electronic structure model that accounts for random alloy fluctuations and connected carrier localisation effects. Our calculations show that in the low temperature regime both the non-radiative Auger-Meitner and radiative recombination rate are strongly impacted by alloy disorder induced carrier localisation effects in these systems. The influence of alloy disorder on the recombination rates is reduced in the high temperature regime, especially for the radiative rate. The Auger-Meitner recombination rate, however, may still be more strongly impacted by alloy disorder when compared to the radiative rate. Our calculations show that while on average radiative recombination slightly increases with increasing temperature, the Auger-Meitner recombination process may, on average, slightly decrease in the temperature range relevant to the thermal efficiency drop (thermal droop). This finding suggests that the considered Auger-Meitner recombination process is unlikely to be directly responsible for the thermal efficiency drop observed experimentally in (Al,Ga)N/AlN quantum well based light emitting devices. Thus, different non-radiative processes, external to the active region, may be the underlying cause of thermal droop in (Al,Ga)N wells.

Ensemble Monte Carlo transport studies of zinc-blende cuprous halides

We present a comprehensive theoretical analysis of intrinsic high-field transport in cuprous halides: CuCl, CuBr, and CuI. Ensemble Monte Carlo transport simulations were performed based on analytical approximations of the multi-valley and three-band electronic structure model. The deformation potentials, extracted from carrier–phonon interaction matrix elements calculated via the Wannier function approach, were employed to determine scattering rates. Our detailed analysis uncovers intriguing transport characteristics based on the complex valence band structures, resulting from spin–orbit coupling and band inversion. Remarkably, the hole mobility in CuI was exceptionally high, reaching up to 193 cm2/V s, while CuCl exhibited unusual temperature dependencies in hole transport. Additionally, the electron mobility in CuI was found to be 254 cm2/V s, indicating a minimal disparity between carrier mobilities, which is advantageous for optoelectronic applications.

Photoinitiated Degradation Kinetics of the Organic UV Filter Oxybenzone in Solutions and Aerosols: Impacts of Salt, Photosensitizers, and the Medium.

Organic UV filters like oxybenzone (BP3) in sunscreens are seawater pollutants suspected to transfer to the atmosphere via sea spray aerosol (SSA). This study examines the photoinitiated degradation of BP3 in artificial and real seawater compared to SSA mimics containing NaCl and 4-benzoylbenzoic acid (4-BBA). We investigated pure, binary, and ternary mixtures of BP3, NaCl, and 4-BBA using solar-simulated light to isolate the effects of salt and photosensitization on BP3 degradation. Results showed significantly faster degradation in the aerosol phase (J eff,env ≈ 10-3-10-2 s-1 or t 1/2 < 10 min) compared to bulk solutions (J eff,env ≈ 10-6 s-1 or t 1/2 > 1 day). The photosensitizer enhanced BP3 photodegradation in both phases more than when mixed with salt or all three components in solutions. BP3 photodegradation was most enhanced by salt in the aerosol phase. High-resolution molecular analysis via Orbitrap LC-MS/MS revealed more acutely toxic compounds (benzophenone, benzoic acid, and benzaldehyde) in irradiated aerosols than in solution, supported by electronic structure and toxicity modeling. These findings highlight that seawater may serve as a reservoir for BP3 and other organic UV filters and that upon transfer into SSA, BP3 rapidly transforms, increasing aerosol toxicity.

Generalizing deep learning electronic structure calculation to the plane-wave basis.

Deep neural networks capable of representing the density functional theory (DFT) Hamiltonian as a function of material structure hold great promise for revolutionizing future electronic structure calculations. However, a notable limitation of previous neural networks is their compatibility solely with the atomic-orbital (AO) basis, excluding the widely used plane-wave (PW) basis. Here we overcome this critical limitation by proposing an accurate and efficient real-space reconstruction method for directly computing AO Hamiltonian matrices from PW DFT results. The reconstruction method is orders of magnitude faster than traditional projection-based methods to convert PW results to the AO basis, and the reconstructed Hamiltonian matrices can faithfully reproduce the PW electronic structure, thus bridging the longstanding gap between the AO basis deep learning electronic structure approach and PW DFT. Advantages of the PW methods, such as high accuracy, high flexibility and wide applicability, thus can be all integrated into deep learning electronic structure methods without sacrificing these methods' inherent benefits. This allows for the construction of large-scale and high-fidelity training datasets with the help of PW DFT results towards the development of precise and broadly applicable deep learning electronic structure models.

Transfer learning relaxation, electronic structure and continuum model for twisted bilayer MoTe2

Large-scale moiré systems are extraordinarily sensitive, with even minute atomic shifts leading to significant changes in electronic structures. Here, we investigate the lattice relaxation effect on moiré band structures in twisted bilayer MoTe2 with two approaches: (a) large-scale plane-wave basis first principle calculation down to 2.88°, (b) transfer learning structure relaxation + local-basis first principles calculation down to 1.1°. We use two types of van der Waals corrections: the D2 method of Grimme and the density-dependent energy correction, and find that the density-dependent energy correction yields a continuous evolution of bandwidth with twist angles. Based on the above results. we develop a complete continuum model with a single set of parameters for a wide range of twist angles, and perform many-body simulations at ν = −1, −2/3, −1/3.

Optical Properties of H-Bonded Heterotriangulene Supramolecular Polymers: Charge-Transfer Excitations Matter.

H-bonded N-heterotriangulene (NHT) supramolecular polymers offer a nice playground to explore the nature and dynamics of electronic excitations in low-dimensional organic nanostructures. Here, we report on a comprehensive molecular modeling of the excited-state electronic structure and optical properties of model NHT stacks, highlighting the important role of intermolecular charge-transfer (CT) excitations in shaping their optical absorption and emission lineshapes. Most importantly, we show that the coupling between the local and CT excitations, modulated by the electric fields induced by the presence of polar amide groups forming H-bonded arrays along the stacks, significantly increases the resulting hybrid exciton bandwidth. We discuss these findings in the context of the efficient transport of singlet excitons over the μm length scale reported experimentally on individual self-assembled nanofibers with molecular-scale diameter.

Transient absorption of warm dense matter created by an X-ray free-electron laser

Warm dense matter is at the boundary between a plasma and a condensed phase and plays a role in astrophysics, planetary science and inertial confinement fusion research. However, its electronic structure and ionic structure upon irradiation with strong laser pulses remain poorly understood. Here, we use an intense and ultrafast X-ray free-electron laser pulse to simultaneously create and characterize warm dense copper using L-edge X-ray absorption spectroscopy over a large irradiation intensity range. Below a pulse intensity of 1015 W cm−2, an absorption peak below the L edge appears, originating from transient depletion of the 3d band. This peak shifts to lower energy with increasing intensity, indicating the movement of the 3d band upon strong X-ray excitation. At higher intensities, substantial ionization and collisions lead to the transition from reverse saturable absorption to saturable absorption of the X-ray free-electron laser pulse, two nonlinear effects that hold promise for X-ray pulse-shaping. We employ theoretical calculations that combine a model based on kinetic Boltzmann equations with finite-temperature real-space density-functional theory to interpret these observations. The results can be used to benchmark non-equilibrium models of electronic structure in warm dense matter.

Ligand-tuning copper in coordination polymers for efficient electrochemical C–C coupling

Cu catalyses electrochemical CO2 reduction to valuable multicarbon products but understanding the structure-function relationship has remained elusive due to the active Cu sites being heterogenized and under dynamic re-construction during electrolysis. We herein coordinate Cu with six phenyl-1H-1,2,3-triazole derivatives to form stable coordination polymer catalysts with homogenized, single-site Cu active sites. Electronic structure modelling, X-ray absorption spectroscopy, and ultraviolet–visible spectroscopy show a widely tuneable Cu electronics by modulating the highest occupied molecular orbital energy of ligands. Using CO diffuse reflectance Fourier transform infrared spectroscopy, in-situ Raman spectroscopy, and density functional theory calculations, we find that the binding strength of *CO intermediate is positively correlated to highest occupied molecular orbital energies of the ligands. As a result, we enable a tuning of C–C coupling efficiency—a parameter we define to evaluate the efficiency of C2 production—in a broad range of 0.26 to 0.86. This work establishes a molecular platform that allows for studying structure-function relationships in CO2 electrolysis and devises new catalyst design strategies appliable to other electrocatalysis.

First-Principles Computational Screening of Two-Dimensional Polar Materials for Photocatalytic Water Splitting.

The band gap constraint of the photocatalyst for overall water splitting limits the utilization of solar energy. A strategy to broaden the range of light absorption is employing a two-dimensional (2D) polar material as photocatalyst, benefiting from the deflection of the energy level due to their intrinsic internal electric field. Here, by using first-principles computational screening, we search for 2D polar semiconductors for photocatalytic water splitting from both ground- and excited-state perspectives. Applying a unique electronic structure model of polar materials, there are 13 photocatalyst candidates for the hydrogen evolution reaction (HER) and 8 candidates for the oxygen evolution reaction (OER) without barrier energies from the perspective of the ground-state free energy variation calculation. In particular, Cu2As4Cl2S3 and Cu2As4Br2S3 can catalyze HER and OER simultaneously, becoming promising photocatalysts for overall water splitting. Furthermore, by combining ground-state band structure calculations with excited-state charge distribution and transfer calculated by linear-response time-dependent density functional theory (LR-TDDFT) and time-dependent ab initio nonadiabatic molecular dynamics (NAMD), respectively, the rationality of the 2D polar material model has been manifested. The intrinsic built-in electric field promotes the separation of charge carriers while suppressing their recombination. Therefore, our computational work provides a high-throughput method to design high-performance photocatalysts for water splitting.

Spectator Exciton Effects in Nanocrystals III: Unveiling the Stimulated Emission Cross Section in Quantum Confined CsPbBr3 Nanocrystals.

Quantifying stimulated emission in semiconductor nanocrystals (NCs) remains challenging due to masking of its effects on pump-probe spectra by excited state absorption and ground state bleaching signals. The absence of this defining photophysical parameter in turn impedes assignment of band edge electronic structure in many of these important fluorophores. Here we employ a generally applicable 3-pulse ultrafast spectroscopic method coined the "Spectator Exciton" (SX) approach to measure stimulated-emission efficiency in quantum confined inorganic perovskite CsPbBr3 NCs, the band edge electronic structure of which is the subject of lively ongoing debate. Our results show that in 5-6 nm CsPbBr3 NCs, a single exciton bleaches more than half of the intense band edge absorption band, while the cross section for stimulated emission from the same state is nearly 6 times weaker. Discussion of these findings in light of several recent electronic structure models for this material proves them unable to simultaneously explain both measures, proving the importance of this new input to resolving this debate. Along with femtosecond time-resolved photoluminescence measurements on the same sample, SX results also verify that biexciton interaction energy is intensely attractive with a magnitude of ∼80 meV. In light of this observation, our previous suggestion that biexciton interaction is repulsive is reassigned to hot phonon induced slowdown of carrier relaxation leading to direct Auger recombination from an excited state. The mechanism behind the extreme slowing of carrier cooling after several stages of exciton recombination remains to be determined.

Twisto-Electrochemical Activity Volcanoes in Trilayer Graphene.

In this work, we develop a twist-dependent electrochemical activity map, combining a low-energy continuum electronic structure model with modified Marcus-Hush-Chidsey kinetics in trilayer graphene. We identify a counterintuitive rate enhancement region spanning the magic angle curve and incommensurate twists in the system geometry. We find a broad activity peak with a ruthenium hexamine redox couple in regions corresponding to both magic angles and incommensurate angles, a result qualitatively distinct from the twisted bilayer case. Flat bands and incommensurability offer new avenues for reaction rate enhancements in electrochemical transformations.

FROG: Exploiting all-atom molecular dynamics trajectories to calculate linear and non-linear optical responses of molecular liquids within Dalton's QM/MM polarizable embedding scheme.

Quantum mechanical/molecular mechanics (QM/MM) methods are interesting to model the impact of a complex environment on the spectroscopic properties of a molecule. In this context, a FROm molecular dynamics to second harmonic Generation (FROG) code is a tool to exploit molecular dynamics trajectories to perform QM/MM calculations of molecular optical properties. FROG stands for "FROm molecular dynamics to second harmonic Generation" since it was developed for the calculations of hyperpolarizabilities. These are relevant to model non-linear optical intensities and compare them with those obtained from second harmonic scattering or second harmonic generation experiments. FROG's specificity is that it is designed to study simple molecular liquids, including solvents or mixtures, from the bulk to the surface. For the QM/MM calculations, FROG relies on the Dalton package: its electronic-structure models, response theory, and polarizable embedding schemes. FROG helps with the global workflow needed to deal with numerous QM/MM calculations: it permits the user to separate the system into QM and MM fragments, to write Dalton's inputs, to manage the submission of QM/MM calculations, to check whether Dalton's calculation finished successfully, and finally to perform averages on relevant QM observables. All molecules within the simulation box and several time steps are tackled within the same workflow. The platform is written in Python and installed as a package. Intermediate data such as local electric fields or individual molecular properties are accessible to the users in the form of Python object arrays. The resulting data are easily extracted, analyzed, and visualized using Python scripts that are provided in tutorials.

Coupled spin-lattice dynamics from the tight-binding electronic structure

We developed a method which performs the coupled adiabatic spin and lattice dynamics based on the tight-binding electronic structure model, where the intrinsic magnetic field and ionic forces are calculated from the converged self-consistent electronic structure at every time step. By doing so, this method allows us to explore limits where the physics described by a parameterized spin-lattice Hamiltonian is no longer accurate. We demonstrate how the lattice dynamics is strongly influenced by the underlying magnetic configuration, where disorder is able to induce significant lattice distortions. The presented method requires significantly less computational resources than methods, such as time-dependent density functional theory (TD-DFT). Compared to parameterized Hamiltonian-based methods, it also describes more accurately the dynamics of the coupled spin and lattice degrees of freedom, which becomes important outside of the regime of small lattice and spin fluctuations. Published by the American Physical Society 2024

Electronic Structures of Passive Film Formed on Ti and Cr in a Phosphate Buffer Solution of pH 7

The electronic structures, including the semiconductive properties, of the passive films formed on Cr and Ti in a phosphate buffer solution of pH 7 were evaluated using photoelectrochemical response, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy (XPS). Based on the results, electronic band structure models of the passive films were proposed: the passive films on Cr consisted of an inner p-type oxide layer with a band gap energy, E g, of 3.6 eV and an outer p-type hydroxide layer with E g of 2.5 eV whereas those on Ti consisted of an inner n-type oxide layer with E g of 3.2 eV and an outer n-type hydroxide layer with E g of 2.5 eV. The type of semiconductor evaluated for the oxide and hydroxide layers was strongly supported by valence-band XPS, which can provide the energy difference between the Fermi energy of the underlying metal and the highest energy of the valence bands of the oxide and hydroxide layers in the passive films.

Quantum oscillations evidence for topological bands in kagome metal ScV6Sn6

Metals with kagome lattice provide bulk materials to host both the flat-band and Dirac electronic dispersions. A new family of kagome metals is recently discovered in AV6Sn6. The Dirac electronic structures of this material needs more experimental evidence to confirm. In the manuscript, we investigate this problem by resolving the quantum oscillations in both electrical transport and magnetization in ScV6Sn6. The revealed orbits are consistent with the electronic band structure models. Furthermore, the Berry phase of a dominating orbit is revealed to be around π, providing direct evidence for the topological band structure, which is consistent with calculations. Our results demonstrate a rich physics and shed light on the correlated topological ground state of this kagome metal.

Statistical model of electronic structure in InAs, InP, GaSb, and Si quantum dots with surface roughness

Simulations based on the sp 3 d 5 s * empirical tight-binding method were performed to provide a statistical understanding of the electronic structures and bandgap distributions of III–V (InAs, InP, GaSb) and IV (Si) semiconductor quantum dots (QDs) with surface roughness. The electronic states and wavefunctions of QDs with surface roughness of different sizes, shapes, and materials were computed. The effects of surface roughness on the electronic structures and the bandgap distributions of QDs were investigated. The results show that the bandgaps of QDs of considered materials/sizes/shapes increase on average when introducing surface roughness. It is shown that the simulated bandgap distributions of QDs with surface roughness can be reproduced by a simple model formula, which can be applied to different materials, sizes, and shapes. The model formula was derived by assuming that removing and adding of one atom procedures are independent random processes.

4f-Orbital mixing increases the magnetic susceptibility of Cp'3Eu.

Traditional models of lanthanide electronic structure suggest that bonding is predominantly ionic, and that covalent orbital mixing is not an important factor in determining magnetic properties. Here, 4f orbital mixing and its impact on the magnetic susceptibility of Cp'3Eu (Cp' = C5H4SiMe3) was analyzed experimentally using magnetometry and X-ray absorption spectroscopy (XAS) methods at the C K-, Eu M5,4-, and L3-edges. Pre-edge features in the experimental and TDDFT-calculated C K-edge XAS spectra provided unequivocal evidence of C 2p and Eu 4f orbital mixing in the π-antibonding orbital of a' symmetry. The charge-transfer configurations resulting from 4f orbital mixing were identified spectroscopically by using Eu M5,4-edge and L3-edge XAS. Modeling of variable-temperature magnetic susceptibility data showed excellent agreement with the XAS results and indicated that increased magnetic susceptibility of Cp'3Eu is due to removal of the degeneracy of the 7F1 excited state due to mixing between the ligand and Eu 4f orbitals.

Towards reliable and efficient modeling of [Cu2O2]2+-based compound electronic structures with the partially fixed reference space protocols.

This work reports a computationally efficient approach for reliable modeling of complex electronic structures based on [Cu2O2]2+ moieties. Specifically, we explore the recently developed partially fixed reference space (PFRS) protocol to minimize the active space size, taking into account the double d-shell effects. We show that the ground-state electronic structure of the core [Cu2O2]2+ model system is dominated by the d9/d10 occupations. The PFRS-crafted active spaces are further used to generate the reference wave functions for the multi-reference coupled cluster, configuration interaction, and multi-reference perturbation theory calculations. Specifically, we demonstrate that the bare [Cu2O2]2+ core can be modeled qualitatively using active spaces as small as CAS(2,2)PFRS. To obtain quantitative agreement with the reference DMRG(32,62)CI calculations, the CAS(4,4) has to be used in conjunction with the MRCCSD correction on top of it. This reliable and computationally efficient protocol is further used to model the electronic structure and properties of ammonia coordinated [Cu2O2]2+ complexes. Finally, based on the large amount of available experimental data regarding the oxo-peroxo equilibrium of [Cu2O2]2+-based systems, it is possible to formulate educated guesses regarding the effect of each experimental variable over each d-occupancy-specific state. With a large sample size of d-occupancy-specific state dependence with ligands and solvents, it should be possible to propose new ligands with specific d-occupancy and, therefore, oxidative properties based on the d-occupancy energy gaps of relatively low-cost calculations.

Enhanced Electrochemical Activity Volcanoes in Flat-Band Twisted Trilayer Graphene

Electrochemical reactions at electrode-electrolyte interfaces are often controlled by modifying the substrate and thereby tuning the adsorption energy to reach peaks of activity volcanoes. In this work, we attempt to enhance interfacial charge transfer kinetics through modifying the electronic density of states of an electrode which offers highly tunable flat bands such as the twisted graphene system, allowing greater overlap with the redox couple states. Correspondingly, we develop a twist-dependent electrochemical activity map, combining a tight-binding electronic structure model with modified Marcus-Hush-Chidsey kinetics in trilayer graphene. We identify a counterintuitive rate enhancement region spanning the magic angle curve and incommensurate twists of the system geometry. At room temperature, we find a broad activity peak with a ruthenium hexamine redox couple in regions corresponding to both magic angles and incommensurate angles, a result qualitatively distinct from the twisted bilayer case. Flat bands and incommensurability offer new avenues for reaction rate enhancements in electrochemical transformations.

PyBEST: Improved functionality and enhanced performance

PyBEST: Improved functionality and enhanced performance