Investigation of the Pd(1-x)Znxalloy phase diagram usingab initiomodelling approaches.

The identification of the stable phases in alloy materials is challenging because composition affects the structural stability of different intermediate phases. Computational simulation, via multiscale modelling approaches, can significantly accelerate the exploration of phase space and help to identify stable phases. Here, we apply such new approaches to understand the complex phase diagram of binary alloys of PdZn, with the relative stability of structural polymorphs considered through application of density functional theory coupled with cluster expansion (CE). The experimental phase diagram has several competing crystal structures, and we focus on three different closed-packed phases that are commonly observed for PdZn, namely the face-centred cubic (FCC), body-centred tetragonal (BCT) and hexagonal close packed (HCP), to identify their respective stability ranges. Our multiscale approach confirms a narrow range of stability for the BCT mixed alloy, within the Zn concentration range from 43.75% to 50%, which aligns with experimental observations. We subsequently use CE to show that the phases are competitive across all concentrations, but with the FCC alloy phase favoured for Zn concentrations below 43.75%, and that the HCP structure favoured for Zn-rich concentrations. Our methodology and results provide a platform for future investigations of PdZn and other close-packed alloy systems with multiscale modelling techniques.

Partial Order-Disorder Transition Driving Closure of Band Gap: Example of Thermoelectric Clathrates.

In the quest for efficient thermoelectrics, semiconducting behavior is a targeted property. Yet, this is often difficult to achieve due to the complex interplay between electronic structure, temperature, and disorder. We find this to be the case for the thermoelectric clathrate Ba_{8}Al_{16}Si_{30}: Although this material exhibits a band gap in its ground state, a temperature-driven partial order-disorder transition leads to its effective closing. This finding is enabled by a novel approach to calculate the temperature-dependent effective band structure of alloys. Our method fully accounts for the effects of short-range order and can be applied to complex alloys with many atoms in the primitive cell, without relying on effective medium approximations.

How a Ferroelectric Layer Can Tune a Two-Dimensional Electron Gas at the Interface of LaInO3 and BaSnO3: A First-Principles Study.

The emerging interest in two-dimensional electron gases (2DEGs), formed at interfaces between two insulating oxide perovskites, poses a crucial fundamental question in view of future electronic devices. In the framework of density-functional theory, we investigate the possibility to control the characteristics of the 2DEG formed at the LaInO3/BaSnO3 interface by including a ferroelectric layer. To do so, we consider BaTiO3 as a prototype example and examine how the orientation of the ferroelectric polarization impacts density and confinement of the 2DEG. We find that aligning the ferroelectric polarization toward (outward) the LaInO3/BaSnO3 interface leads to an accumulation (depletion) of the interfacial 2DEG. Varying its magnitude, we find a linear effect on the 2DEG charge density that is confined within the BaSnO3 side. Analysis of the optimized geometries reveals that inclusion of the ferroelectric layer makes structural distortions at the LaInO3/BaSnO3 junction less pronounced, which, in turn, enhances the 2DEG density. Thicker ferroelectric layers allow for reaching higher polarization magnitude. We discuss the mechanisms behind all these findings and rationalize how the characteristics of both 2DEGs and 2D hole gases can be controlled in the considered heterostructures. Overall, our results can be generalized to other combinations of ferroelectric, polar, and nonpolar materials.

DFT exchange: sharing perspectives on the workhorse of quantum chemistry and materials science.

In this paper, the history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners. The format of the paper is that of a roundtable discussion, in which the participants express and exchange views on DFT in the form of 302 individual contributions, formulated as responses to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper represents a broad snapshot of DFT, anno 2022.

Density-of-states similarity descriptor for unsupervised learning from materials data.

We develop a materials descriptor based on the electronic density-of-states (DOS) and investigate the similarity of materials based on it. As an application example, we study the Computational 2D Materials Database (C2DB) that hosts thousands of two-dimensional materials with their properties calculated by density-functional theory. Combining our descriptor with a clustering algorithm, we identify groups of materials with similar electronic structure. We introduce additional descriptors to characterize these clusters in terms of crystal structures, atomic compositions, and electronic configurations of their members. This allows us to rationalize the found (dis)similarities and to perform an automated exploratory and confirmatory analysis of the C2DB data. From this analysis, we find that the majority of clusters consist of isoelectronic materials sharing crystal symmetry, but we also identify outliers, i.e., materials whose similarity cannot be explained in this way.

All-electron many-body approach to resonant inelastic X-ray scattering.

We present a formalism for the resonant inelastic X-ray scattering (RIXS) cross section. The resulting compact expression in terms of polarizability matrix elements, particularly lends itself to the implementation in an all-electron many-body perturbation theory (MBPT) framework, which is realized in the full-potential package exciting. With the carbon K edge RIXS of diamond and the oxygen K edge RIXS of ß-Ga2O3, respectively, we demonstrate the importance of electron-hole correlation and atomic coherence in the RIXS spectra.

Chirality of Valley Excitons in Monolayer Transition-Metal Dichalcogenides.

By enabling control of valley degrees of freedom in transition-metal dichalcogenides, valley-selective circular dichroism has become a key concept in valleytronics. Herein, we show that valley excitons, bound electron-hole pairs formed at the K or K̅ valleys upon absorption of circularly polarized light, are chiral quasiparticles characterized by a finite orbital angular momentum (OAM). We further formulate an ab initio many-body theory of valley-selective circular dichroism and valley excitons based on the Bethe-Salpeter equation. Besides governing the interaction with circularly polarized light, the OAM confers upon excitons a finite magnetization that manifests itself through an excitonic Zeeman splitting upon interaction with external magnetic fields. The good agreement between our ab initio calculations and recent experimental measurements of the exciton Zeeman shifts corroborates this picture, indicating that valley excitons can carry angular momentum even in their singlet state.

FAIR data enabling new horizons for materials research.

The prosperity and lifestyle of our society are very much governed by achievements in condensed matter physics, chemistry and materials science, because new products for sectors such as energy, the environment, health, mobility and information technology (IT) rely largely on improved or even new materials. Examples include solid-state lighting, touchscreens, batteries, implants, drug delivery and many more. The enormous amount of research data produced every day in these fields represents a gold mine of the twenty-first century. This gold mine is, however, of little value if these data are not comprehensively characterized and made available. How can we refine this feedstock; that is, turn data into knowledge and value? For this, a FAIR (findable, accessible, interoperable and reusable) data infrastructure is a must. Only then can data be readily shared and explored using data analytics and artificial intelligence (AI) methods. Making data 'findable and AI ready' (a forward-looking interpretation of the acronym) will change the way in which science is carried out today. In this Perspective, we discuss how we can prepare to make this happen for the field of materials science.

The Collaborative Research Center FONDA.

Today's scientific data analysis very often requires complex Data Analysis Workflows (DAWs) executed over distributed computational infrastructures, e.g., clusters. Much research effort is devoted to the tuning and performance optimization of specific workflows for specific clusters. However, an arguably even more important problem for accelerating research is the reduction of development, adaptation, and maintenance times of DAWs. We describe the design and setup of the Collaborative Research Center (CRC) 1404 "FONDA -- Foundations of Workflows for Large-Scale Scientific Data Analysis", in which roughly 50 researchers jointly investigate new technologies, algorithms, and models to increase the portability, adaptability, and dependability of DAWs executed over distributed infrastructures. We describe the motivation behind our project, explain its underlying core concepts, introduce FONDA's internal structure, and sketch our vision for the future of workflow-based scientific data analysis. We also describe some lessons learned during the "making of" a CRC in Computer Science with strong interdisciplinary components, with the aim to foster similar endeavors.

OPTIMADE, an API for exchanging materials data.

The Open Databases Integration for Materials Design (OPTIMADE) consortium has designed a universal application programming interface (API) to make materials databases accessible and interoperable. We outline the first stable release of the specification, v1.0, which is already supported by many leading databases and several software packages. We illustrate the advantages of the OPTIMADE API through worked examples on each of the public materials databases that support the full API specification.

Accessing the Anisotropic Nonthermal Phonon Populations in Black Phosphorus.

We combine ultrafast electron diffuse scattering experiments and first-principles calculations of the coupled electron-phonon dynamics to provide a detailed momentum-resolved picture of lattice thermalization in black phosphorus. The measurements reveal the emergence of highly anisotropic nonthermal phonon populations persisting for several picoseconds after exciting the electrons with a light pulse. Ultrafast dynamics simulations based on the time-dependent Boltzmann formalism are supplemented by calculations of the structure factor, defining an approach to reproduce the experimental signatures of nonequilibrium structural dynamics. The combination of experiments and theory enables us to identify highly anisotropic electron-phonon scattering processes as the primary driving force of the nonequilibrium lattice dynamics in black phosphorus. Our approach paves the way toward unravelling and controlling microscopic energy flows in two-dimensional materials and van der Waals heterostructures, and may be extended to other nonequilibrium phenomena involving coupled electron-phonon dynamics such as superconductivity, phase transitions, or polaron physics.

Spatial Confinement as an Effective Strategy for Improving the Catalytic Selectivity in Acetylene Hydrogenation.

While control over chemical reactions is largely achieved by altering the intrinsic properties of catalysts, novel strategies are constantly being proposed to improve the catalytic performance in an extrinsic way. Since the fundamental chemical behavior of molecules can remarkably change when their molecular scale is comparable to the size of the space where they are located, creating spatially confined environments around the active sites offers new means of regulating the catalytic processes. We demonstrate through first-principles calculations that acetylene hydrogenation can exhibit significantly improved selectivity within the confined sub-nanospace between two-dimensional (2D) monolayers and the Pd(111) substrate. Upon intercalation of molecules, the lifting and undulation of a 2D monolayer on Pd(111) influence the adsorption energies of intermediates to varying extents, which, in turn, changes the energy profiles of the hydrogenation reactions. Within the confined sub-nanospace, the formation of ethane is always unfavorable, demonstrating effective suppression of the unwanted overhydrogenation. Moreover, the catalytic properties can be further tuned by altering the coverage of the adsorbates as well as strains within the 2D monolayer. Our results also indicate that for improving the selectivity, the strategy of spatial confinement could not be combined with that of single-atom catalysis, since the reactant molecules cannot enter the sub-nanospace due to the too weak adsorbate-substrate interaction. This work sheds new light on designing novel catalysts with extraordinary performance for the selective hydrogenation of acetylene.

Ultrafast Hot Phonon Dynamics in MgB_{2} Driven by Anisotropic Electron-Phonon Coupling.

The zone-center E_{2g} modes play a crucial role in MgB_{2}, controlling the scattering mechanisms in the normal state as well the superconducting pairing. Here, we demonstrate via first-principles quantum-field theory calculations that, due to the anisotropic electron-phonon interaction, a hot-phonon regime where the E_{2g} phonons can achieve significantly larger effective populations than other modes, is triggered in MgB_{2} by the interaction with an ultrashort laser pulse. Spectral signatures of this scenario in ultrafast pump-probe Raman spectroscopy are discussed in detail, revealing also a fundamental role of nonadiabatic processes in the optical features of the E_{2g} mode.

Hybrid Organic-Inorganic Perovskites as Promising Substrates for Pt Single-Atom Catalysts.

Single-atom catalysts (SACs) combine the best of two worlds by bridging heterogeneous and homogeneous catalysis. The superior catalytic properties of SACs, however, can hardly be exploited without a suitable substrate. Here, we explore the possibility of using hybrid organic-inorganic perovskites as supporting materials for single transition-metal atoms. By means of first-principles calculations, we predict that single Pt atoms can be incorporated into methylammonium lead iodide surfaces by replacing the methylammonium groups at the outermost layer. The iodide anions at the surface provide potentially uniform anchoring sites for the Pt atoms and donate electrons, generating negatively charged Pt_{1}^{δ-} species that allow for preferential O_{2} adsorption in the presence of CO. Such Pt sites are able to catalyze CO oxidation and may also play a role in CO_{2} reduction. The fundamental understanding generated here will shed light on potential applications of hybrid perovskites in the field of (photo)catalysis.

Polarized absorbance and Davydov splitting in bulk and thin-film pentacene polymorphs.

Pentacene is one of the most studied organic materials and in particular its optical properties have been the subject of intense research during the last two decades. In spite of such a widespread interest and of the extensive knowledge achieved so far, a number of issues are still debated. One of the most relevant questions concerns the role of polymorphism and how it affects the lowest-energy exciton, which appears in the visible region and is subject to a sizable Davydov splitting. We address this problem in a combined theoretical and experimental work, where the optical absorption properties of three pentacene polymorphs are investigated within the whole energy range of visible light. Optical spectra computed from first principles in the framework of many-body perturbation theory are directly compared with the polarization-resolved absorbance, measured for three different pentacene phases (the two bulk polymorphs and the thin-film phase). In this way, we unambiguously identify the two Davydov components of the first exciton and the optical fingerprints of each considered phase. With very good agreement between theory and experiment, we show that all polymorphs exhibit common features at the absorption onset, while phase-dependent characteristics appear only above 2 eV. We discuss the character of the lowest-lying singlet and triplet excitons, including dark ones, highlighting the contributions from the electronic bands and the role of the electron-hole interaction and of the local-field effects.

Molecular structure of the substrate-induced thin-film phase of tetracene.

We present a combined experimental and theoretical study to solve the unit-cell and molecular arrangement of the tetracene thin film (TF) phase. TF phases, also known as substrate induced phases (SIPs), are polymorphs that exist at interfaces and decisively impact the functionality of organic thin films, e.g., in a transistor channel, but also change the optical spectra due to the different molecular packing. As SIPs only exist in textured ultrathin films, their structure determination remains challenging compared to bulk materials. Here, we use grazing incidence X-ray diffraction and atomistic simulations to extract the TF unit-cell parameters of tetracene together with the atomic positions within the unit-cell.

The LDA-1/2 Method Applied to Atoms and Molecules.

The LDA-1/2 method evaluates ionization potentials as the energy of the highest occupied molecular orbitals (HOMOs) at half occupation. It has proven to be a viable approach for calculating band gaps of semiconductors. To address its accuracy for finite systems, we apply LDA-1/2 to the atoms and molecules of the GW100 test set. The obtained HOMO energies are validated against CCSD(T) data and the G0 W0 approach of many-body perturbation theory. The accuracy of LDA-1/2 and G0 W0 is found to be the same, where the latter is computationally much more involved. To get insight into the benefits and limitations of the LDA-1/2 method, we analyze the impact of each assumption made in deriving the methodology.

Carbon nitride supported Fe2 cluster catalysts with superior performance for alkene epoxidation.

Sub-nano metal clusters often exhibit unique and unexpected properties, which make them particularly attractive as catalysts. Herein, we report a "precursor-preselected" wet-chemistry strategy to synthesize highly dispersed Fe2 clusters that are supported on mesoporous carbon nitride (mpg-C3N4). The obtained Fe2/mpg-C3N4 sample exhibits superior catalytic performance for the epoxidation of trans-stilbene to trans-stilbene oxide, showing outstanding selectivity of 93% at high conversion of 91%. Molecular oxygen is the only oxidant and no aldehyde is used as co-reagent. Under the same condition, by contrast, iron porphyrin, single-atom Fe, and small Fe nanoparticles (ca. 3 nm) are nearly reactively inert. First-principles calculations reveal that the unique reactivity of the Fe2 clusters originates from the formation of active oxygen species. The general applicability of the synthesis approach is further demonstrated by producing other diatomic clusters like Pd2 and Ir2, which lays the foundation for discovering diatomic cluster catalysts.