Structure Search Research Articles

Structural Disorder by Octahedral Tilting in Inorganic Halide Perovskites: New Insight with Bayesian Optimization

Structural disorder is common in metal‐halide perovskites and important for understanding the functional properties of these materials. First‐principles methods can address structure variation on the atomistic scale, but they are often limited by the lack of structure‐sampling schemes required to characterize the disorder. Herein, structural disorder in the benchmark inorganic halide perovskites CsPbI3 and CsPbBr3 is computationally studied in terms of the three octahedral‐tilting angles. The subsequent variations in energetics and properties are described by 3D potential‐energy surfaces (PESs) and property landscapes, delivered by Bayesian optimization as implemented in the Bayesian optimization structure search code sampling density functional theory (DFT) calculations. The rapid convergence of the PES with about 200 DFT data points in 3D searches demonstrates the power of active learning and strategic sampling with Bayesian optimization. Further analysis indicates that disorder grows with increasing temperature and reveals that the material bandgap at finite temperatures is a statistical mean over disordered structures.

Pressure-induced phase transitions of ZrAl2 from first-principles calculations

Although ZrAl2 has been extensively studied, its structural features and properties under high pressures remain unclear. Using the CALYPSO structural search method combined with first-principles calculations, we investigated the structural evolution and mechanical stability of ZrAl2 at high pressures. Our research reveals that at 198 GPa, ZrAl2 undergoes a phase transition from the P63/mmc phase to the Pmmm phase. This transition results in a volume collapse of 2.1%, indicating a first-order phase change. A comprehensive analysis of the elastic constants and phonon spectra confirms the structural stability of four new phases of ZrAl2. Our research findings provide a comprehensive view of the structural evolution of ZrAl2 under high pressure. This valuable information enhances the understanding of the physical and chemical properties of C14-type ZrAl2 when subjected to high-pressure conditions.

Geometric and electronic properties of anionic precious metal gold doped boron clusters AuB n − (n = 10–20)

Recently, the Au–B covalent bonds in gold doped boron clusters has attracted great attention. However, there are fewer theoretical reports on exploration their ground state structures and stabilities, especially for the medium sizes. Here, we study the structural evolution and electronic properties of the anionic Au doped boron clusters with medium sizes of n from 10 to 20 using the unbiased cluster structural searches combined with density functional theory (DFT) calculations. The results reveal that the quasi-planar AuB18 − (1A, C 1) cluster shows excellent stability and a large vertical separation energy (VDE) of 4.25 eV. The good consistency between the computationally simulated photoelectron spectra and the experimental spectra strongly supports the correctness of our low-lying structures. Further bonding analyses show that the well-stabilized aromatic AuB18 − cluster is due to the active σ interactions between Au atom (6s orbitals) and B units (2p orbitals), as well as the large number of σ–bonds in the B18 − moiety with π-aromaticity. These findings enriched the family of Au-B alloy clusters and metal-doped boron-based aromatic clusters, which provide valuable information for the experimental characterization and preparation of boron-rich alloy nanoclusters in the future.

Structural evolution and electronic properties of anionic plutonium-doped oxygen clusters

Plutonium oxides are important in actinide chemistry and nuclear industry activities, and the demand and interest in enriching knowledge of plutonium chemistry is growing increasingly significant. However, unlike uranium oxide clusters, few studies related to the geometry and bonding properties of anionic plutonium oxide clusters have been reported. Here we explored the geometries, photoelectron spectra, and electronic properties of anionic plutonium oxide clusters by means of unbiased structural searches coupled with density-functional theory (DFT). The results show that the PuO6− cluster with a high D2h symmetry formed by a linear O-Pu-O plutonyl unit with two O2 units exhibits excellent stability. In addition, the HOMO–LUMO gap value of PuO6− cluster are 4.35 eV and 3.41 eV for the α- and β-orbitals, respectively, as well as the vertical detachment energy (VDE) of 4.20 eV. In the analysis of molecular orbitals and adaptive natural density partitioning in oxygen-rich systems, the σ bonds between plutonium atom and oxygen ligands, primarily from the Pu-5f and O-2p orbitals, are responsible for the goodish stability of PuO6− cluster. We hope that the current work can enrich the geometrical configuration of plutonium oxide oxygen clusters and provide reference information for the subsequent research work.

Pressure-Induced Re-Entrant Superconductivity in Transition Metal Dichalcogenide TiSe2.

Transition metal dichalcogenide TiSe2 exhibits a superconducting dome within a low pressure range of 2-4GPa, which peaks with the maximal transition temperature Tc of ≈1.8 K. Here it is reported that applying high pressure induces a new superconducting state in TiSe2, which starts at ≈16GPa with a substantially higher Tc that reaches 5.6 K at ≈21.5GPa with no sign of decline. Combining high-throughput first-principles structure search, X-ray diffraction, and Raman spectroscopy measurements up to 30GPa, It is found that TiSe2 undergoes a first-order structural transition from the 1T phase under ambient pressure to a new 4O phase under high pressure. Comparative ab initio calculations reveal that while the conventional phonon-mediated pairing mechanism may account for the superconductivity observed in 1T-TiSe2 under low pressure, the electron-phonon coupling of 4O-TiSe2 is too weak to induce a superconducting state whose transition temperature is as high as 5.6 K under high pressure. The new superconducting state found in pressurized TiSe2 requires further study on its underlying mechanism.

Novel ground state structures of N-doped LuH3

Ab-initio crystal structure searches have played a pivotal role in recent discoveries of high-Tc hydride superconductors under high pressure. Using evolutionary crystal searches, we predict novel ground state structures of N-doped LuH3 at ambient conditions. We find an insulating ground state structure for LuN0.125H2.875 (∼1.0 wt.% N), contrary to earlier studies where assumed structures were all metallic. This insulating behavior of ground state was found to persist up to ∼45 GPa. However our crystal structure searches revealed a metallic state for an H-deficient variant of LuN0.125H2.875. We study bonding characteristics of important structures by calculating electronic density of states, electronic-localization functions and Bader charges. Our Bader charge analysis shows that insulators have both H+ and H− ions whereas metals have only H− ions. We find that H+ ions are bonded to N atoms via a very short covalent bond. Thus we identify a clear relationship between formation of N–H bonds and insulating behavior of materials. Besides this, we perform crystal structure searches for three more compositions with higher N-content (>1.0 wt.%). Analysis of electronic properties shows that the ground states of these compositions are insulator.

Non-emergency department (ED) interventions to reduce ED utilization: a scoping review

BackgroundEmergency department (ED) crowding is a global burden. Interventions to reduce ED utilization have been widely discussed in the literature, but previous reviews have mainly focused on specific interventions or patient groups within the EDs. The purpose of this scoping review was to identify, summarize, and categorize the various types of non-ED-based interventions designed to reduce unnecessary visits to EDs.MethodsThis scoping review followed the JBI Manual for Evidence Synthesis and the PRISMA-SCR checklist. A comprehensive structured literature search was performed in the databases MEDLINE and Embase from 2008 to March 2024. The inclusion criteria covered studies reporting on interventions outside the ED that aimed to reduce ED visits. Two reviewers independently screened the records and categorized the included articles by intervention type, location, and population.ResultsAmong the 15,324 screened records, we included 210 studies, comprising 183 intervention studies and 27 systematic reviews. In the primary studies, care coordination/case management or other care programs were the most commonly examined out of 15 different intervention categories. The majority of interventions took place in clinics or medical centers, in patients’ homes, followed by hospitals and primary care settings - and targeted patients with specific medical conditions.ConclusionA large number of studies have been published investigating interventions to mitigate the influx of patients to EDs. Many of these targeted patients with specific medical conditions, frequent users and high-risk patients. Further research is needed to address other high prevalent groups in the ED - including older adults and mental health patients (who are ill but may not need the ED). There is also room for further research on new interventions to reduce ED utilization in low-acuity patients and in the general patient population.

Large-Gap Quantum Spin Hall Insulators in Two-Dimensional Hafnium Halides: Unraveling the Impact of Strain and Substrate.

Two-dimensional (2D) topological insulators (TIs) or quantum spin Hall (QSH) insulators, characterized by insulating 2D electronic band structures and metallic helical edge states protected by time-reversal symmetry, offer a platform for realizing the quantum spin Hall effect, making them promising candidates for future spintronic devices and quantum computing. However, observing a high-temperature quantum spin Hall effect requires large-gap 2D TIs, and only a few 2D systems have been experimentally confirmed to possess this property. In this study, we employ first-principles calculations, combined with a structural search based on an evolutionary algorithm, to predict a class of 2D QSH insulators in hafnium halides, namely, HfF, HfCl, and HfBr with sizable band gaps of 0.12, 0.19, and 0.38 eV. Their topological nontrivial nature is confirmed by a Z2 invariant which equals to 1 and the presence of gapless edge states. Furthermore, the QSH effect in these materials remains robust under biaxial tensile strain of up to 10%, and the use of h-BN as a substrate effectively preserves the QSH states in these materials. Our findings pave the way for future theoretical and experimental investigations of 2D hafnium halides and their potential for realizing the QSH effect.

A Machine-Learning-Assisted Crystalline Structure Prediction Framework To Accelerate Materials Discovery.

Modern crystal structure prediction methods based on structure generation algorithms and first-principles calculations play important roles in the design of new materials. However, the cost of these methods is very expensive because their success mostly relies on the efficient sampling of structures and the accurate evaluation of energies for those sampled structures. Herein, we develop a Machine-learning-Assisted CRYStalline Materials sAmpling sysTem (MAXMAT) aiming to accelerate the prediction of new crystal structures. For a given chemical composition, MAXMAT can generate efficient crystal structures with the help of a Python package for crystal structure generation (PyXtal) and can quickly evaluate the energies of these generated structures using a well-developed machine learning interaction potential model (M3GNET). We have used MAXMAT to perform crystal structure searches for three different chemical systems (TiO2, MgAl2O4, and BaBOF3) to test its accuracy and efficiency. Furthermore, we apply MAXMAT to predict new nonlinear optical materials, suggesting several thermodynamically synthesizable structures with high performance in LiZnGaS3 and CaBOF3 systems.

Accelerating structure search using atomistic graph-based classifiers.

We introduce an atomistic classifier based on a combination of spectral graph theory and a Voronoi tessellation method. This classifier allows for the discrimination between structures from different minima of a potential energy surface, making it a useful tool for sorting through large datasets of atomic systems. We incorporate the classifier as a filtering method in the Global Optimization with First-principles Energy Expressions (GOFEE) algorithm. Here, it is used to filter out structures from exploited regions of the potential energy landscape, whereby the risk of stagnation during the searches is lowered. We demonstrate the usefulness of the classifier by solving the global optimization problem of two-dimensional pyroxene, three-dimensional olivine, Au12, and Lennard-Jones LJ55 and LJ75 nanoparticles.

Vascular access specialist teams versus standard practice for catheter insertion and prevention of failure: a systematic review

ObjectiveBillions of vascular access devices (VADs) are inserted annually for intravenous therapy worldwide. However, their use is not without challenges. Facilitating the process and enhancing results, hospital authorities have created...

Atomic-scale perspective on individual thiol-terminated molecules anchored to single S vacancies in MoS2

Sulfur vacancies in MoS2 on Au(111) have been shown to be negatively charged as reflected by a Kondo resonance. Here, we use scanning tunneling microscopy to show that these vacancies serve as anchoring sites for thiol-based molecules (CF3−3P−SH) with two distinct reaction products, one of them showing a Kondo resonance. Based on comparisons with density-functional theory (DFT) calculations, including a random structure search and computation of energies and electronic properties at a hybrid exchange-correlation functional level, we conclude that both anchored molecules are charge neutral. We propose that one of them is an anchored intact CF3−3P−SH molecule while the other one is the result of catalytically activated dehydrogenation to CF3−3P−S with subsequent anchoring. Our investigations highlight a perspective of functionalizing defects with thiol-terminated molecules that can be equipped with additional functional groups, such as charge donor or acceptor moieties, switching units, or magnetic centers. Published by the American Physical Society 2024

Systematic search of circular structures using satellite imagery to identify potential new impact structures in Mauritania

Mauritania, with its ancient (Archean to Paleoproterozoic) and desertic terrains and gentle relief, has been under-explored in terms of impact structures. To date, two confirmed impact craters, namely Tenoumer and Aouelloul, and four circular structures for which an impact origin has been suggested, are known in Mauritania. This work aims at a systematic exploration of circular structures in Mauritania and provide a comprehensive database to support their exploration and elucidate their origin. This approach includes multi-scale search on Google Earth images, and a preliminary assessment of their origin using available geological, geophysical, and geochemical data as well as Digital Elevation Models. A total of 50 new circular structures were detected during our survey, adding to four candidates previously identified. They are distributed throughout the territory with an important fraction of them being located in the Taoudeni basin. The diameters of these structures vary from 60 m to 7.5 km with a right-skewed distribution. A preliminary assessment of the possible origins of these circular structures is proposed and the most promising candidates for potential meteoritic impact sites are listed for future investigations.

Real-Time Classification Model of Public Emergencies Using Fusion Expansion Network

In today's deep learning-dominated era, real-time classification of public emergencies is a critical research area. Existing methods, however, often fall short in considering both temporal and spatial aspects comprehensively. This study introduces GEDNAS, a novel model that combines atrous convolutional neural network (DCNN), gated recurrent unit (GRU), and neural structure search (NAS) to address these limitations. GEDNAS utilizes DCNN to capture local spatio-temporal features, integrates GRU for time series modeling, and employs NAS for overall structural optimization. The approach significantly enhances real-time public emergency classification performance, showcasing its efficiency and accuracy in responding to real-time scenarios and providing robust support for emergency response efforts. This research introduces an innovative solution for public safety, advancing the application of deep learning in emergency management and inspiring the design of real-time classification models, ultimately enhancing overall societal safety.

Theoretical exploration of novel compounds in Sr(B,C)x (x = 7,8) at high pressure

Boron-carbon-based compounds have attracted considerable attention due to their exceptional properties and increasing applications in industry. In this study, we conducted a systematic structural prediction of the SrBxC7-x and SrBxC8-x systems under ambient and high pressures up to 20 GPa using an unbiased global structure search. Through the calculations of formation enthalpy and phonon dispersion curves, we identified three new compounds, namely SrB5C2, SrB6C and SrB5C3, as thermodynamically and dynamically stable under ambient pressure and high pressures up to 20 GPa. Calculations of mechanical properties reveal that these three compounds have significant mechanical strength, with estimated theoretical Vickers hardness values ranging from 23.2 to 39.8 GPa. Electronic structure calculations suggest that both SrB5C2 and SrB5C3 are hole conductors, with the bands crossing the Fermi level, and SrB6C is a semiconductor with an indirect bandgap of 2.4 eV. The electron-phonon coupling calculations using the Migdal-Eliashberg theory indicate that SrB5C2 exhibits superconductivity at 10.5 K under ambient pressure, while SrB5C3 shows superconductivity at a much lower temperature of 0.4 K. This finding adds to our knowledge of boron-carbide materials and provides valuable insights for the development of similar materials with good mechanical properties.

Hund’s three rules in actinide-containing superatoms with spin-orbit coupling calculations

The intriguing and challenge issue in magnetic superatoms is searching for the suitable candidates to validate the Hund’s rules. Here, early actinide elements (An: Ac, Th, Pa, U, Np, Pu, Am) whose 5f electrons may crossover the localization and delocalization characteristics have been chosen to alloy with Al atoms in designing magnetic An@Al12 superatoms. By doing the global minimum structure search and the spin-orbital coupling density functional theory calculations, we provide an original idea to give theoretical argument that Hund’s three rules are still applicable in superatoms, which can be related to the fillings of highly localized An-5f orbitals into large exchange-splitting 2 F superatom orbitals. Specifically, selective 5f sub-orbitals of several An dopants can exhibit a dual nature in superatomic bonding, i.e. partial 5f electrons of Pa, U and Pu are reactive whereas all 5f electrons of Np and Am are highly localized. The molecular orbital analyses, combined with the qualitative interpretation of the phenomenological superatom sub-shell model, address the intricate interplays between the structure symmetry, electronic structure, spin and orbital magnetic moments. These findings have important implications for understanding the bonding and magnetic behaviors of An-containing superatoms and pave the way for designing novel magnetic superatoms.

Pressure-induced evolution of structures and phase transition of technetium diboride

Using the particle swarm optimization algorithm, we conducted an extensive search for the high-pressure stable structure of technetium diboride (TcB2) within the pressure range of 0–400 GPa. At zero pressure, the P63/mmc (hP6-TcB2) structure is considered the ground state configuration. As the pressure increases, a structural transition from hP6-TcB2 to P6/mmm (hP3-TcB2) occurs at approximately 174.9 GPa. We discuss the bonding between the two distinct phases and analyze the contribution of different atomic bonds to maintaining their structural stability. Meanwhile, the temperature–pressure phase diagram of TcB2 was successfully determined for the first time through the quasi-harmonic approximation method. It is predicted that the transition pressure from hP6-TcB2 to hP3-TcB2 can be reduced to about 164 GPa at a room temperature of 300 K. These results provide valuable insights into the behavior of TcB2 under different temperature and pressure conditions and open up new possibilities for exploring its potential applications in a variety of environments.

Theoretical Determination of the Electronic Structures and Energy-Level Splitting for Pr3+-Doped Y2SiO5 Crystals.

Trivalent praseodymium (Pr3+)-doped yttrium silicate (Y2SiO5) crystals have been widely used in various phosphors owing to their excellent luminescence characteristics. Although a series of studies have been carried out on its application prospects, the electronic structures and energy-transfer mechanisms of Pr3+-doped Y2SiO5 (Y2SiO5:Pr) remain an exploratory topic. Herein, the crystal structure analysis by the particle swarm optimization structure search method is used to study the structural evolution of Y2SiO5:Pr. Two novel structures with local [PrO7]-11 and [PrO6]-9 [Y2SiO5:Pr (I) and Y2SiO5:Pr (II)] are successfully identified. The impurity Pr3+ ions occupy the Y3+ sites and successfully integrate into the Y2SiO5 host crystal with a Pr3+ concentration of 6.25%. The calculated electronic band structures show that the doping of Pr3+ induces a reduction in band gaps for the host Y2SiO5 crystal. The conduction bands near the Fermi level are completely composed of f states. For the atomic energies of Pr3+ in Y2SiO5, the Stark levels and transitions are properly simulated based on a new set of crystal field parameters (CFPs) at the C1 site symmetry. A satisfactory r.m.s. dev. of 15.57 cm-1 with 9 free ion parameters (plus 27 fixed CFPs as obtained from ab initio calculation) fitted to the 33 observed levels is obtained for the first time. The plentiful energy-level transition lines, from the visible light to the near-infrared region, are deciphered for Pr3+ in Y2SiO5. Blue 3P0 → 3H4 at 465 nm is calculated to be a strong emission line, and it might be an ideal channel for laser actions. These results could not only provide important insights into the rare-earth-doped crystals but also lay the foundation for future research studies of designing the new laser materials.

A terpenoids database with the chemical content as a novel agronomic trait.

Natural products play a pivotal role in drug discovery, and the richness of natural products, albeit significantly influenced by various environmental factors, is predominantly determined by intrinsic genetics of a series of enzymatic reactions and produced as secondary metabolites of organisms. Heretofore, few natural product-related databases take the chemical content into consideration as a prominent property. To gain unique insights into the quantitative diversity of natural products, we have developed the first TerPenoids database embedded with Content information (TPCN) with features such as compound browsing, structural search, scaffold analysis, similarity analysis and data download. This database can be accessed through a web-based computational toolkit available at http://www.tpcn.pro/. By conducting meticulous manual searches and analyzing over 10 000 reference papers, the TPCN database has successfully integrated 6383 terpenoids obtained from 1254 distinct plant species. The database encompasses exhaustive details including isolation parts, comprehensive molecule structures, chemical abstracts service registry number (CAS number) and 7508 content descriptions. The TPCN database accentuates both the qualitative and quantitative dimensions as invaluable phenotypic characteristics of natural products that have undergone genetic evolution. By acting as an indispensable criterion, the TPCN database facilitates the discovery of drug alternatives with high content and the selection of high-yield medicinal plant species or phylogenetic alternatives, thereby fostering sustainable, cost-effective and environmentally friendly drug discovery in pharmaceutical farming. Database URL: http://www.tpcn.pro/.

Unexpected thermal transport properties of MgSiO3 monolayer at extreme conditions

The thermal transport properties of mantle minerals are of paramount importance to understand the thermal evolution processes of the Earth. Here, we perform extensively structural searches of two-dimensional MgSiO3 monolayer by CALYPSO method and first-principles calculations. A stable MgSiO3 monolayer with Pmm2 symmetry is uncovered, which possesses a wide indirect band gap of 4.39 eV. The calculations indicate the lattice thermal conductivities of MgSiO3 monolayer are 49.86 W (mK)−1 and 9.09 W (mK)−1 in x and y directions at room temperature. Our findings suggest that MgSiO3 monolayer is an excellent low-dimensional thermoelectric material with high ZT value of 4.58 from n-type doping in the y direction at 2000 K. The unexpected anisotropic thermal transport of MgSiO3 monolayer is due to the puckered crystal structure and the asymmetric phonon dispersion as well as the distinct electron states around the Fermi level. These results offer a detailed description of structural and thermal transport properties of MgSiO3 monolayer at extreme conditions.