Atomic Properties Research Articles

Structural and bonding characteristics in Au2Ge9ˉ and Au2Ge10ˉ clusters: Insights from photoelectron spectroscopy and theoretical calculations

Germanium-based materials exhibit promising properties for applications in electronics, sensing, and catalysis. Gold-germanium clusters are of particular interest due to their potential for enhanced stability and tailored electronic properties. This study investigates the structures, bonding, and electronic properties of Au2Ge9ˉ and Au2Ge10ˉ clusters using anion photoelectron spectroscopy and theoretical calculations. The clusters were generated using laser vaporization and studied using anion photoelectron spectroscopy. Theoretical calculations employed density functional theory and coupled-cluster methods. Au2Ge9ˉ and Au2Ge10ˉ clusters exhibit weak aurophilic interactions between the two gold atoms. The gold atoms mimic the electronic and structural properties of germanium atoms, acting as surrogates within the cluster framework. Understanding the role of gold in these germanium clusters provides insights for designing novel materials with tailored properties for applications in catalysis, electronics, and other fields.

Investigating the Structural, Electronic and Magnetic Properties of Single Vanadium Atom Doped Germanene Monolayer using Density Functional Theory (DFT)

In this study, density functional theory (DFT) within generalized gradient approximation (GGA) as implemented in Quantum ESPRESSO package has been employed. The structural, electronic, and magnetic properties of single Vanadium atom (V)-doped germanene monolayer have been investigated. The doping is carried out in 2x2x1 supercell with 32 atoms which gives around 3.12% doping concentration. The results revealed that single V atom doped Germanene monolayer induced both ferromagnetic and antiferromagnetic behavior with total magnetic moment of about 0.77 μB and 1.95 μB respectively. Also the behavior of the pristine germanene remains unaffected by the single V doping. The stability of the doped system are investigated by calculating cohesive and binding energies. These results are in good agreement with many reported results in case of both graphene and silicene. It’s also suggested that, the single V-doped germanene monolayer can support the quantum anomalous Hall effect, which has significant potential for spintronic applications.Keyword: Density Functional Theory (DFT), Generalized Gradient Approximation (GGA), Structural, Electronic and Magnetic Properties, Doping, Germanene Monolayer

Photoionization process of the hydrogenlike carbon ion embedded in warm and hot dense plasmas.

Complicated many-body interactions between ions and surrounding particles exist in warm and hot dense plasmas. It will significantly alter the atomic structures and dynamic properties of the embedded ions. Recently, the atomic-state-dependent (ASD) screening model has been proposed and shown to be valid for investigating the screening effect in warm and hot dense plasmas over a wide range of electron densities and temperatures. By employing the ASD model, we investigate the photoionization process for the hydrogenlike carbon ion embedded in warm and hot dense plasmas with corresponding Coulomb coupling parameter ranges of 0.05 ≤ Γ ≤ 1.16, where Γ characterizes the ratio of the average potential to thermal energy. It is found that there are stronger plasma screening effects on the ionization energy and photoionization cross section due to the negative-energy electron distributions considered in the ASD model compared to those considering only free electrons. The present results from the ASD model show reasonable agreement with the classical Debye-Hückel (DH) model in weakly coupled plasmas. However, significant deviations of the ionization energy and cross section between these two models are observed in moderately and strongly coupled plasmas, due to the approximate treatment of the plasma-electron density distribution of the DH model. In the region of low photoelectron energies, the positions of the shape resonance peaks of the cross sections obtained from the ASD model differ significantly from those of the DH model due to the different screening effects.

Emergence of two distinct phase transitions in monolayer CoSe2 on graphene

Dimensional modifications play a crucial role in various applications, especially in the context of device miniaturization, giving rise to novel quantum phenomena. The many-body dynamics induced by dimensional modifications, including electron-electron, electron-phonon, electron-magnon and electron-plasmon coupling, are known to significantly affect the atomic and electronic properties of the materials. By reducing the dimensionality of orthorhombic CoSe2 and forming heterostructure with bilayer graphene using molecular beam epitaxy, we unveil the emergence of two types of phase transitions through angle-resolved photoemission spectroscopy and scanning tunneling microscopy measurements. We disclose that the 2 × 1 superstructure is associated with charge density wave induced by Fermi surface nesting, characterized by a transition temperature of 340 K. Additionally, another phase transition at temperature of 160 K based on temperature dependent gap evolution are observed with renormalized electronic structure induced by electron-boson coupling. These discoveries of the electronic and atomic modifications, influenced by electron-electron and electron-boson interactions, underscore that many-body physics play significant roles in understanding low-dimensional properties of non-van der Waals Co-chalcogenides and related heterostructures.Graphical

Performance assessment of the effective core potentials under the fermionic neural network: First and second row elements.

The rapid development of deep learning techniques has driven the emergence of a neural network-based variational Monte Carlo (VMC) method (referred to as FermiNet), which has manifested high accuracy and strong predictive power in the electronic structure calculations of atoms, molecules, and some periodic systems. Recently, the implementation of the effective core potential (ECP) scheme has further facilitated more efficient calculations in practice. However, there is still a lack of comprehensive assessments of the ECP's performance under the FermiNet. In this work, we set sail to fill this gap by conducting extensive tests on the first two row elements regarding their atomic, spectral, and molecular properties. Our major finding is that, in general, the qualities of ECPs have been correctly reflected under FermiNet. Two recently built ECP tables, namely, correlation consistent ECP (ccECP) and energy consistent correlated electron pseudopotential (eCEPP), seem to prevail in terms of overall performance. In particular, ccECP performs slightly better on spectral precision and covers more elements, while eCEPP is more systematically built from both shape and energy consistency and better treats the core polarization. On the other hand, the high accuracy of the all-electron calculations is hindered by the absence of relativistic effects as well as the numerical instabilities in some heavier elements. Finally, with further in-depth discussions, we generate possible directions for developing and improving FermiNet in the near future.

Spray Angle and Uniformity of the Flat Fan Nozzle of Deep Loosener Fertilizer for Intra-Soil Application of Fertilizers

This paper deals with the problem of predetermining the spray angle and uniformity of the flat fan sprayer with a semicircular impact surface for the intra-soil application of liquid mineral fertilizers. The jet impact on a round splash plate and radial atomization properties are investigated theoretically, the formation features of the spray with an obtuse angle are studied in a geometrical way, and the design search of the nozzle shape and optimization calculations are performed using computational fluid dynamics (CFD) simulations and then verified experimentally. It was revealed that the spray rate and spray angle can be adjusted by changing the parameter s, and when the spray angle is within s = 0–0.2 mm, it forms spray angles with range of 140°–175°. The spraying angle, in turn, shows the potential length of the tillage knife in accordance with the undersoil cavity dimensions. A spray uniformity of up to 74% was achieved, which is sufficient for applied studies and for intra-soil application operations. According to the investigations and field experiments, it can be concluded that the designed nozzle is applicable for the intra-soil application of liquid mineral fertilizers. The use of flat fan nozzles that form a spraying band under the soil cavity and along the entire length of the tillage knife ensures a highly efficient mixing process, the liquid mineral fertilizers with treated soil (particles) positively contributing to plant maturation.

Rearranging Spin Electrons by Axial-Ligand-Induced Orbital Splitting to Regulate Enzymatic Activity of Single-Atom Nanozyme with Destructive d-π Conjugation.

Most of the nanozymes have been obtained based on trial and error, for which the application is usually compromised by enzymatic activity regulation due to a vague catalytic mechanism. Herein, a hollow axial Mo-Pt single-atom nanozyme (H-MoN5@PtN4/C) is constructed by a two-tier template capture strategy. The axial ligand can induce Mo 4d orbital splitting, leading to a rearrangement of spin electrons (↑ ↑ → ↑↓) to regulate enzymatic activity. This creates catalase-like activity and enhances oxidase-like activity to catalyze cascade enzymatic reactions (H2O2 → O2 → O2•-), which can overcome tumor hypoxia and accumulate cytotoxic superoxide radicals (O2•-). Significantly, H-MoN5@PtN4/C displays destructive d-π conjugation between the metal and substrate to attenuate the restriction of orbitals and electrons. This markedly improves enzymatic performance (catalase-like and oxidase-like activity) of a Mo single atom and peroxidase-like properties of a Pt single atom. Furthermore, the H-MoN5@PtN4/C can deplete overexpressed glutathione (GSH) through a redox reaction, which can avoid consumption of ROS (O2•- and •OH). As a result, H-MoN5@PtN4/C can overcome limitations of a complex tumor microenvironment (TME) for tumor-specific therapy based on TME-activated catalytic activity.

New dispersion mechanism for oxide dispersion-strengthened steels by liquid metallurgy

The use of oxide dispersion-strengthened (ODS) alloys in demanding applications can effectively reduce parts’ weights, extend life of use, and enhance overall energy efficiency. But, the current manufacturing of ODS alloys has remained impractical for decades due to poor scalability and extremely high costs. Mass production of ODS steels by liquid metallurgy is therefore crucial to decrease their costs by several orders of magnitude and expand their potential applications. However, oxide nanoparticle (NP) dispersion in molten alloys presents fundamental challenges for liquid metallurgy due to the vastly dissimilar atomic properties between ionocovalent oxides and metals. Here we show, for the first time, that Y2O3 NPs are able to be dispersed in liquid 316L with a 1 % Nb addition. It was discovered that Nb-enriched interfacial layers exist around the Y2O3 NPs in solidified steels after slow cooling. Theoretical analyses reveal that the Nb-enriched interfacial layer induces a higher energy barrier and a significantly lower van der Waals attraction between oxide NPs and liquid Fe for the successful dispersion of oxide NPs in liquid steels. Moreover, Y2O3 and Al2O3 NPs were successfully dispersed in lean steels, such as Fe-Nb and low-C steels. This new dispersion mechanism of oxide NPs opens an exciting pathway for the economical mass manufacturing of various ODS alloys by liquid metallurgy for numerous applications.

From structure to surface tension of small silicon clusters by Quantum Monte Carlo simulations

We investigate the structural, surface and electronic properties of small silicon clusters Sin (for n=2 to 15) using HF, DFT and FN-DMC calculations. We analyze the atomic configurations, surface properties and electronic structures and show that the radius and average surface area of the clusters can be modeled by a Jellium-type model. We found that the surface tension σ of the clusters decreases with increasing cluster size in the range of the clusters under investigation. An estimate of the surface tension for bulk silicon yields σbulk=0.88(3) J/m2 in agreement with recent experiments. The average bond length of the clusters shows a non-monotonic behavior. Smaller clusters exhibit a high spin state influenced by electron correlation, especially during the 2D to 3D structural transition, which occurs at n=4 to n=5. We also find that the Si4, Si10 and Si12 clusters exhibit enhanced stability due to electron correlation. Our results are consistent with the experiments on bond length, binding energy and dissociation energy.

Regular relations of the composition, structure and properties of crystals of hydrogen-containing compounds

Research subject. Crystals of hydrogen-containing compounds belonging to the superprotonic family. Aim. To obtain knowledge about regular relations between composition, atomic structure, real structure and physical properties of materials, with the purpose of elucidating processes occurring in condensed state and forming the basis for modification of known or obtaining new compounds. Materials and methods. Experimental data were obtained using a set of complementary physical methods, including structural analysis using X-rays, synchrotron radiation and neutrons, optical microscopy, and atomic force microscopy. Results. Experimental data on the atomic structure, real structure, and physical properties of superprotonic crystals, including systems of hydrogen bonds and their changes, were obtained. Conclusions. The physical properties of superprotonic crystals are significantly affected by hydrogen bonding systems and their changes, primarily by the formation of dynamically disordered hydrogen bonds with energetically equivalent positions of hydrogen atoms. When carrying out diagnostics of crystalline samples, account should be taken of their real structure, including the structure of surface layers and the presence of crystallization water. These factors may affect the measured physical parameters, the boundaries of existence of phases, the formation of a multiphase state under variations in temperature.

Short-range-order degree dominated physical and mechanical properties of refractory multi-principal element alloys: a first-principles study

The degree of short-range order (SRO) can influence the physical and mechanical properties of refractory multi-principal element alloys (RMPEAs). Here, the effect of SRO degree on the atomic configuration and properties of the equiatomic TiTaZr RMPEA is investigated using the first-principles calculations. Their key roles on the lattice parameters, binding energy, elastic properties, electronic structure, and stacking fault energy (SFE) are analyzed. The results show the degree of SRO has a significant effect on the physical and mechanical properties of TiTaZr. During the SRO degree increasing in TiTaZr lattice, the low SRO degree exacerbates the lattice distortion and the high SRO degree reduces the lattice distortion. The high degree of SRO improves the binding energy and elastic stiffness of the TiTaZr. By analyzing the change in charge density, this change is caused by the atomic bias generated during the formation of the SRO, which leading to a change in charge-density thereby affecting the metal bond polarity and inter-atomic forces. The high SRO degree also reduces SFE, which means the capability of plastic deformation of the TiTaZr is enhanced.

N-Heterocyclic Carbene Monolayers on Metal-Oxide Films: Correlations between Adsorption Mode and Surface Functionality.

N-Heterocyclic carbene (NHC) ligands have been self-assembled on various metal and semimetal surfaces, creating a covalent bond with surface metal atoms that led to high thermal and chemical stability of the self-assembled monolayer. This study explores the self-assembly of NHCs on metal-oxide films (CuOx, FeOx, and TiOx) and reveals that the properties of these metal-oxide substrates play a pivotal role in dictating the adsorption behavior of NHCs, influencing the decomposition route of the monolayer and its impact on work function values. While the attachment of NHCs onto CuOx is via coordination with surface oxygen atoms, NHCs interact with TiOx through coordination with surface metal atoms and with FeOx via coordination with both metal and oxygen surface atoms. These distinct binding modes arise due to variances in the electronic properties of the metal atoms within the investigated metal-oxide films. Contact angle and ultraviolet photoelectron spectroscopy measurements have shown a significantly higher impact of F-NHC adsorption on CuOx than on TiOx and FeOx , correlated to a preferred, averaged upright orientation of F-NHC on CuOx.

Density functional theory study on interatomic forces and electronic properties of ConMoP(n = 1 ~ 5) cluster

AbstractTo delve into the microscopic property variations of the ConMoP(n = 1 ~ 5) cluster, this study employs density functional theory at the B3LYP/def2‐TZVP quantum chemistry level. The paper conducts a comprehensive theoretical analysis of the clusters, examining parameters such as bond lengths, bond angles, electronic localization function (ELF), interaction region indicator function (IRI), independent gradient model based on the Hirshfeld partition, deformation density, electronic space range, chemical hardness and softness, polarizability, and dipole moment. The optimization process reveals 16 stable configurations for the ConMoP(n = 1 ~ 5) cluster, predominantly taking on a steric form. As the cluster size increases, the electronic delocalization of Co atoms intensifies, while the electronic properties of Mo atoms remain relatively stable. Notably, P atoms maintain a high degree of electronic delocalization. The interatomic forces within the clusters predominantly exhibit covalent bonding, with no evident repulsive effects observed between atoms. The bonding between metal atoms in the clusters leans toward a preference for covalent interaction. The degree of dispersion in the clusters increases with their growth, particularly evident in configuration 5‐a, which displays a broader spatial distribution. Configuration 3‐a demonstrates the most favorable activity, showcasing a relatively stable structure. Overall, configuration 3‐a emerges as a focal point for catalytic reactions. This article provides a more comprehensive analysis of the ConMoP(n = 1 ~ 5) cluster, yielding diverse results and enhancing the theoretical understanding of this cluster.

Chemically functionalized AlN quantum dots for effective sensing and removal of methanol, ethanol, and formaldehyde: A first principle study

In this study, we delve into the structural and electronic intricacies of 2D aluminum nitride quantum dots (AlN-QDs) and their derivatives. Through detailed analysis, we uncover notable variations in bond lengths upon passivation with elements such as fluorine (F) and hydroxyl (OH) groups, with the latter exhibiting a particularly intriguing stability profile with a binding energy of 5.171 eV. Our investigation reveals a substantial energy gap of ∼5 eV in AlN-QDs, indicating enhanced electron confinement and optimal conditions for semiconductor applications. Furthermore, we elucidate the electron donation properties of nitrogen atoms and electron acceptance tendencies of aluminum atoms within AlN-QDs, shedding light on their unique electronic structure. Quantum stability assessments unveil charge distribution asymmetries and variations in electronegativity, contributing to a deeper understanding of AlN-QDs' robustness. We also demonstrate a significant enhancement in electrical conductivity, notably with AlN-QDs-surf-2CO exhibiting remarkable performance. Additionally, our study showcases AlN-QDs-OH's exceptional adsorption capabilities, evidenced by significantly higher adsorption energies for small organic compounds, highlighting their potential as highly effective sensors. Optical investigations further reinforce these findings, revealing distinct shifts in absorption spectra upon adsorption, which underscore the substantial impact of adsorbates on AlN-QDs' optical properties

ZORA Basis Sets of 5 and 6 Zeta Valence Qualities for H-Ar: Application in Calculations of Atomic and Molecular Properties

ZORA Basis Sets of 5 and 6 Zeta Valence Qualities for H-Ar: Application in Calculations of Atomic and Molecular Properties

Effects of Alloying Element on Hydrogen Adsorption and Diffusion on α-Fe(110) Surfaces: First Principles Study

Based on first principles density functional theory (DFT) methods, this study employed the Cambridge Serial Total Energy Package (CASTEP) module within Materials Studio (MS) software under the generalized gradient approximation to investigate the adsorption, diffusion behavior, and electronic properties of hydrogen atoms on α-Fe(110) and α-Fe(110)-Me (Mn, Cr, Ni, Mo) surfaces, including calculations of their adsorption energies and density of states (DOS). The results demonstrated that doping with alloy atoms Me increased the physical adsorption energy of H2 molecules on the surface. Specifically, Mo doping elevated the adsorption energy from −1.00825 eV to −0.70226 eV, with the largest relative change being 30.35%. After doping with Me, the chemical adsorption energy of two hydrogen atoms does not change significantly, among which doping with Cr results in a decrease in the chemical adsorption energy. Building on this, further analysis of the chemical adsorption of single atoms on the surface was conducted. By comparing the adsorption energy and the bond length between a hydrogen atom and iron/dopant metal atom, it was found that Mo doping has the greatest impact, increasing the bond length by 58.58%. Analysis of the DOS functions under different doping conditions validated the interaction between different alloy elements and H atoms. Simultaneously, simulations were carried out on the energy barrier crossed by H atoms diffusing into the metal interior. The results indicate that Ni doping facilitates the diffusion of H atoms, while Cr, Mn, and Mo hinder their diffusion, with Mo having the most significant effect, where its barrier is 21.88 times that of the undoped surface. This conclusion offers deep insights into the impact of different doping elements on hydrogen adsorption and diffusion, aiding in the design of materials resistant to hydrogen embrittlement.

Performance and mechanism of atomizing dust removal from APG12/Active Water: Experimental and molecular simulation study

Coal mining processes produce large amounts of dust particles that seriously pollute the environment and threaten health. Spraying technology is a primary technique for dust removal. To date, experimental methods are mainly applied to study the atomization and dust removal properties of water droplets, but the intermolecular mechanism involved is unclear. First, a test platform was assembled to evaluate the atomization and dust removal performance of APG12/active water. Then, APG12 droplet and APG12 droplet/anthracite molecular models were constructed, and the underlying mechanism was elucidated through molecular simulation. The experimental results showed that the droplet diameter of the APG12/active water spray decreased by 14.15%, and the dust removal efficiencies of total dust and respirable dust increased by 39.55% and 61.51%, respectively. The simulation results indicated that APG12 molecules and H2O molecules exhibited attractive interactions. This interaction weakened the electrostatic attraction between the H2O molecules in the APG12/active water droplets. Moreover, the interaction enhanced the repulsive van der Waals interactions, reduced the number of hydrogen bonds, and increased the diffusion coefficient of H2O molecules. As a result, the droplets were relatively easy to break. In addition, APG12 molecules covered the surfaces of anthracite molecules, thus increasing the surface oxygen content and the electrostatic attraction, van der Waals forces and hydrogen bonding between H2O and coal molecules. This enhancement, in turn, improved the wettability of coal dust. Herein, the molecular mechanism of dust removal from APG12/active water was analysed, providing guidance for the development of new dust suppressants.

Multi-pulse Ramsey interferometry of a double-well Bose–Einstein condensate in a cavity

Ramsey interferometry as one of the most important high-precision measurement methods has prospects for inferring various properties of ultracold atoms and molecules. We investigate the multi-pulse Ramsey interferometry of a double-well Bose–Einstein condensate (BEC) in an optical cavity. Compared with the standard two-pulse Ramsey scheme, our multi-pulse Ramsey proposal greatly relaxes the requirements for both intensity and width of the pulses, allowing the interferometry to be achieved using weak and narrow pulses. When the pumping pulses characterizing the coupling between the cavity field and the atomic BEC are applied to the zero background field, we demonstrate the atomic Ramsey fringes in the time domain for different pulse numbers and different pulse widths. We find that although the multi-pulse Ramsey fringes are no longer sensitive to cavity-pump detuning, they can still record the information of the interaction between coherent atoms. We obtain the fundamental frequency of the multi-pulse Ramsey fringes analytically and find that it is proportional to the number of pulses. Particularly, it is shown that the minimum of the fundamental frequency is exactly the critical point of the phase transition of the system. For a nonzero background field, the results indicate that a nondestructive observation of atomic Ramsey fringes by cavity transmission spectroscopy is feasible. Our findings provide insights for improving the accuracy of Ramsey interferometry and for using interferometry to observe phase transitions.

Phase change memory materials: Why are alloys of Ge, Sb, and Te the materials of choice?

Rewritable optical storage is dominated by alloys of a small number of elements, particularly Ge, Sb, and Te, and Ge/Sb/Te alloys in the composition range (GeTe)1−x(Sb2Te3)x (0 ≤ x ≤ 1) have been the materials of choice: all have metastable rock salt structures that change little over decades at archival temperatures, and all contain vacancies (cavities). The special status arises from the close similarity of the valence orbitals of Ge, Sb, and Te, which arises from the irregular changes in atomic orbitals and properties as the atomic number increases (“secondary periodicity”). The instability of cubic (metallic) Bi to a (semimetallic) rhombohedral structure (H. Jones, 1934) can be adapted to Ge/Sb/Te alloys and explains the crucial metastable (rock salt) structures of these compounds. Vacancies almost always occur next to Te atoms, which form one sublattice of the rock salt structure.

Relativistic calculations of energy levels, lifetimes, transition parameters, and electron impact excitation cross sections for Kr XIX

In this study, we present a detailed analysis of atomic properties for Kr XIX, specifically focusing on the lowest 128 fine-structure levels originating from the 3s23p6, 3s23p53d, 3s3p63d and 3s23p43d2 configurations. We report energy levels, lifetimes, wavelengths, weighted oscillator strengths, and transition probabilities for multipole transition types (E1, E2, M1, and M2). To achieve this, we employed the GRASP2018 code, which implements the fully relativistic multiconfigurational Dirac–Hartree–Fock method and accounts for Breit interaction and quantum electrodynamic effects. We performed another set of calculations using the many-body perturbation theory implemented in the flexible atomic code (FAC). By comparing the results obtained from GRASP2018 and FAC, we established the accuracy and consistency of our calculations. Furthermore, using the relativistic distorted wave theory, we studied electron impact excitation of all transitions to upper levels from the ground and metastable levels and reported excitation cross sections for incident electron energies up to 5 keV. To enhance the practical utility of our findings, we also provided analytical fittings of these cross sections and excitation rate coefficients for their applications in plasma modeling. This work contributes to the atomic properties and excitation cross sections of Kr XIX, addressing a marked gap in the available atomic data.