K-shell Research Articles

High‐Spin and Reactive Fe13 Cluster with Exposed Metal Sites

AbstractAtomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*4W4Fe13S12, displaying a Fe13 core with M−M bonds that has precedent only in main group and late metal chemistry. M13 clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*4W4Fe13S12 displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.

High-Spin and Reactive Fe13 Cluster with Exposed Metal Sites.

Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*4 W4 Fe13 S12 , displaying a Fe13 core with M-M bonds that has precedent only in main group and late metal chemistry. M13 clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*4 W4 Fe13 S12 displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.

Enhanced antidiabetic and antioxidant properties of gold nanoparticles green synthesized using blossom extract of Azadirachta indica: In vitro studies

This study describes the in situ biosynthesis of gold nanoparticles (AuNPs) using neem blossom (Azadirachta indica) extract with enhanced in vitro anti-diabetic and antioxidant properties. The formation of AuNPs was confirmed by the characteristic optical response through the surface plasmon resonance (SPR) band observed around 530 nm. The effect of phytochemical in the formation of AuNPs was investigated using Fourier-transform infrared spectroscopy (FTIR). The effect of reaction parameters such as temperature, pH and precursor concentration on the size and surface morphology of AuNPs was optimized using the SPR band. The metallic form of phytosynthesised AuNPs was confirmed by X-ray photoelectron spectra (XPS) results with a distinctive binding energy difference of 4f shells ΔE = 3.8 eV. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) studies confirmed the crystalline nature of the particles formed. The antioxidant property of AuNPs demonstrated the influence of phytochemical surfactants coated on the surface of AuNPs and the results revealed the higher antioxidant (90 %) efficiency compared to standard ascorbic acid. phytosynthesised AuNPs demonstrated 79 % enzyme inhibition efficiency in α-amylase assays. The antimicrobial evaluation results revealed the exceptional microbicidal efficacy of AuNPs against both gram-positive and gram-negative bacteria. Phytochemically activated AuNPs showed improved antioxidant, antimicrobial and antidiabetic properties and it could be a promising candidate for biological applications in medicine.

Relativistic effects on the chemistry of heavier elements: why not given proper importance in chemistry education at the undergraduate and postgraduate level?

Abstract Relativistic effects are important to understand the chemistry of heavier elements across the periodic table (PT). Three important relativistic effects are: contraction of s- and p-orbitals (direct relativistic effect), expansion of d- and f-orbitals (indirect relativistic effect) and spin–orbit (SO) coupling to split the p-, d- and f-orbitals. Each of these effects is approximately proportional to Z 2 (Z = atomic number) for the valence shell electrons in many electron atoms and consequently, these relativistic effects dominantly control the properties of the heavier elements (mainly the 6th and 7th period elements). These aspects are not given the proper importance in most of the inorganic chemistry text books and in chemistry education at the university level.

A unified description of atomic physics for electron Fokker–Planck calculations

Most realistic kinetic calculations for tokamak plasmas are now required to incorporate the effect of partially ionized high-Z elements arising either from uncontrolled influxes of metallic impurities, such as tungsten in high input power regimes or from mitigation of runaway electrons generated after possible major disruptions by massive gas injection. The usual electron–ion Fokker–Planck collision operator must therefore be modified, because all plasma atoms are not entirely ionized, as is the case for light elements. This represents a challenge, in order to perform fast but also accurate calculations, regardless of the type of element present in the plasma, but also their local levels of ionization while covering a wide range of electron energies in a consistent way, from a few keV to tens of MeV in plasmas whose electron temperature may itself vary from 10 eV to several keV. In this context, a unified description of the atomic models is proposed, based on a multi-Yukawa representation of the electrostatic potential calibrated against results obtained by advanced quantum calculations. Besides the possibility to improve the description of inner and outer atomic shells in the determination of the atomic form factor, this model allows one to derive analytical formulations for both elastic and inelastic scattering, which can then be easily incorporated in kinetic calculations. The impact of the number of exponentials in the description of the atomic potential is discussed, and a comparison with simple and advanced atomic models is also performed.

Single‐Atom Zinc Sites with Synergetic Multiple Coordination Shells for Electrochemical H2O2 Production

AbstractPrecise manipulation of the coordination environment of single‐atom catalysts (SACs), particularly the simultaneous engineering of multiple coordination shells, is crucial to maximize their catalytic performance but remains challenging. Herein, we present a general two‐step strategy to fabricate a series of hollow carbon‐based SACs featuring asymmetric Zn−N2O2 moieties simultaneously modulated with S atoms in higher coordination shells of Zn centers (n≥2; designated as Zn−N2O2−S). Systematic analyses demonstrate that the synergetic effects between the N2O2 species in the first coordination shell and the S atoms in higher coordination shells lead to robust discrete Zn sites with the optimal electronic structure for selective O2 reduction to H2O2. Remarkably, the Zn−N2O2 moiety with S atoms in the second coordination shell possesses a nearly ideal Gibbs free energy for the key OOH* intermediate, which favors the formation and desorption of OOH* on Zn sites for H2O2 generation. Consequently, the Zn−N2O2−S SAC exhibits impressive electrochemical H2O2 production performance with high selectivity of 96 %. Even at a high current density of 80 mA cm−2 in the flow cell, it shows a high H2O2 production rate of 6.924 mol gcat−1 h−1 with an average Faradaic efficiency of 93.1 %, and excellent durability over 65 h.

Single-Atom Zinc Sites with Synergetic Multiple Coordination Shells for Electrochemical H2 O2 Production.

Precise manipulation of the coordination environment of single-atom catalysts (SACs), particularly the simultaneous engineering of multiple coordination shells, is crucial to maximize their catalytic performance but remains challenging. Herein, we present a general two-step strategy to fabricate a series of hollow carbon-based SACs featuring asymmetric Zn-N2 O2 moieties simultaneously modulated with S atoms in higher coordination shells of Zn centers (n≥2; designated as Zn-N2 O2 -S). Systematic analyses demonstrate that the synergetic effects between the N2 O2 species in the first coordination shell and the S atoms in higher coordination shells lead to robust discrete Zn sites with the optimal electronic structure for selective O2 reduction to H2 O2 . Remarkably, the Zn-N2 O2 moiety with S atoms in the second coordination shell possesses a nearly ideal Gibbs free energy for the key OOH* intermediate, which favors the formation and desorption of OOH* on Zn sites for H2 O2 generation. Consequently, the Zn-N2 O2 -S SAC exhibits impressive electrochemical H2 O2 production performance with high selectivity of 96 %. Even at a high current density of 80 mA cm-2 in the flow cell, it shows a high H2 O2 production rate of 6.924 mol gcat -1 h-1 with an average Faradaic efficiency of 93.1 %, and excellent durability over 65 h.

Tailoring of electromagnetic properties of arc-produced carbon-coated FeNi alloy nanocapsules for highly efficient microwave absorption

Due to the growing harm of electromagnetic radiation, it is extremely urgent to develop high-efficiency microwave absorbers with tunable electromagnetic properties. Herein, a simple strategy for synthesizing hetero-atoms (sulfur) doped carbon-coated FeNi alloy nanocapsules (FeNi@C(Sx) NCs) by DC arc-discharge plasma was demonstrated. The hetero-interface between the FeNi alloy core and the graphitic shell induce interfacial polarization was found. Meantime, many defects produced by substitutional sulfur atoms in the graphitic shell facilitated dipole polarization and conduction loss. Besides, the multiple magnetic resonance produced by FeNi magnetic alloys worked together to optimize impedance matching. The excellent microwave absorption performance was attributed to the core-shell structure, dipole and interface polarizations, as well as favorable impedance matching. Importantly, the first-principles calculation was applied to prove the charge transfer and polarization process. The minimum reflection loss (RL) can reach up to −50.3 dB at a thickness of 1.6 mm.

Super weak Electromagnetic Radiation in Bio and Inorganic Systems

This article provides a comparative analysis of data on ultra-weak electromagnetic radiation (WEEM) obtained at different times from bio and inorganic systems. The unifying physical principle was the presence of hybrid orbitals in the outer electron shells in the systems under study and the generation of coherent radiation in them. The data of a model experiment on ultra weak radiation of metals and semiconductors in the long-wavelength region of the optical spectrum are presented, indirectly confirming this hypothesis.

SAFE Credit Union Performing Arts Center audio enhancement to support architecture

Opened in 1976 and without a major renovation since, the 98,000-sf SAFE Credit Union Performing Arts Center was in dire need of transformation. The building’s aging infrastructure needed a comprehensive modernization to meet accessibility requirements, the escalating requirements of contemporary performance, and to present a new face to the public as the premier cultural institution in the state capital. The existing theater’s acoustics represented a challenge to effectively accommodate the wide range of performance types including Broadway roadshows, the Sacramento Choral Society, and the Sacramento Philharmonic and Opera. Major renovations work included a complete exterior renovation; new mechanical, plumbing, electrical, and theatrical systems; and substantial updates to the interior finishes throughout the building. Providing an accessible venue to all patrons and performers was the primary goal of the project. Significant modifications to the external and internal circulation included removal of the entire audience chamber floor and new seating and aisle ways throughout. An electro-acoustic enhancement system was designed to provide an acoustically tunable audience chamber and electronic shell on stage to meet all the needs of the resident companies. Design and implementation of the electro-acoustic enhancement system will be discussed, including challenges of performer buy-in and audio orchestra shell integration.

Nonlinear Optical Mechanism of β‐BaB2O4 Revealed by Experimental Electron Density

AbstractNonlinear optical (NLO) materials are of immense scientific and technological importance. However, debate has long prevailed theoretically regarding the structural origin of the second harmonic generation (SHG) effect. In this work, the experimental electron density (ED) of controversial β‐BaB2O4 (BBO) is studied by high‐resolution X‐ray diffraction, indicating that the [B3O6]3− motif dominates two large non‐zero SHG tensors (d222 and d311) while Ba atoms contribute mostly to the smallest one (d333), and the atomic SHG contributions of terminal O atoms in [B3O6]3− motifs are much larger than those of B and bridged O atoms, clarifying the disputes on its NLO response mechanism. Besides, the contraction of inner electron shells (5s25p6) of the Ba atom and partial covalent behavior of the Ba─O interaction are first observed experimentally. Furthermore, the SHG coefficients of BBO derived from experimental ED are in excellent agreement with those from bulk crystals, providing a high‐efficient and low‐cost method of screening high‐performance NLO materials with just an easy‐to‐obtain tiny crystal.

Atomic Electron Shell Excitations in Double-β Decay

The problem of the transition of electron shells of atoms to excited states in the process of neutrinoless double-beta decay is investigated. This subject is crucial for modeling the energy spectrum of beta -electrons, which is sensitive to the mass and Majorana nature of neutrinos. The dependence of the obtained results on the atomic number indicates an important role of the Feinberg–Migdal effect in the electron shell excitations. We report the overlap amplitudes of the electron shells of the parent atom and the daughter ion for eleven atoms, the two-neutrino double-beta decay of which was observed experimentally. In around one-fourth of the cases where the structure of the electron shells is inherited from the parent atom, there is a transition to the ground state or the excited state with the lowest energy. The de-excitation of the daughter ion in the latter scenario is accompanied by the emission of photons in the ultraviolet range, which can serve as an auxiliary signature of double-beta decay. The average excitation energy of the electron shells ranges between 300 and 800 eV, with the variance ranging from (1.7 keV)2 in calcium to (14 keV)2 in uranium.

Tailoring magnesium-based hydrides as potential and reversible materials for solid-state hydrogen storage: A first-principles study

Hydrogen is a promising candidate for green energy sources for future endeavors because of its abundance on Earth. Although its storage is a major challenge for the researchers of this era because of its unsafe and highly explosive nature. The structural, optoelectronic, thermoelectric, vibrational, thermodynamic properties and hydrogen storage capacity of XMgH3 ([Formula: see text], Ba) are carried out by using the full potential linearized augmented plane wave (FP-LAPW) method in the DFT framework. The theoretical study about these magnesium-based metal hydride perovskites, i.e., SrMgH3 and BaMgH3, declares them structurally stable compounds in space group Pm-3m. The optimization graph for SrMgH3 and BaMgH3 reflects the lowest ground state energy, i.e., −6759[Formula: see text]Ry and −16683[Formula: see text]Ry, respectively. Comparatively, BaMgH3 seems to be more stable. The electronic band structures and density of states declare them pure metallic due to zero band gap and overlapping of electronic states of the valence and the conduction bands. The electrical conductivity of BaMgH3 increases up to [Formula: see text] and thermal conductivity [Formula: see text] in the temperature range 100[Formula: see text]K to 1000[Formula: see text]K revealing the good metallic character of BaMgH3. The optical analysis portrays the absorption of compounds in the visible range along with valance shell electrons to the weak bond of hydrogen and dissociates hydrogen molecules at a certain intensity of light. BaMgH3 compound shows minimum scattering and maximum absorption of light in the visible region up to 3[Formula: see text]eV. The reflectivity peaks in the visible region 3.0[Formula: see text]eV show that 40% of light energy is absorbed due to the opaque nature of BaMgH3. Both these compounds are declared thermodynamically stable due to negative free energy such as −1.20[Formula: see text]eV for SrMgH3 and −1.50[Formula: see text]eV energy for BaMgH3 at 1000[Formula: see text]K, respectively. Moreover, the three acoustic modes showing zero imaginary phonon frequencies at [Formula: see text] symmetry points predict these compounds’ structural and thermodynamical stability. The gravimetric hydrogen storage concentration of SrMgH3 and BaMgH3 is determined as 2.637% and 1.836%, respectively.

Investigating mechanisms of state localization in highly ionized dense plasmas.

We present experimental observations of K_{β} emission from highly charged Mg ions at solid density, driven by intense x rays from a free electron laser. The presence of K_{β} emission indicates the n=3 atomic shell is relocalized for high charge states, providing an upper constraint on the depression of the ionization potential. We explore the process of state relocalization in dense plasmas from first principles using finite-temperature density functional theory alongside a wave-function localization metric, and find excellent agreement with experimental results.

Spin-lattice-dynamics analysis of magnetic properties of iron under compression

Compression of a magnetic material leads to a change in its magnetic properties. We examine this effect using spin-lattice dynamics for the special case of bcc-Fe, using both single- and poly-crystalline Fe and a bicontinuous nanofoam structure. We find that during the elastic phase of compression, the magnetization increases due to a higher population of the nearest-neighbor shell of atoms and the resulting higher exchange interaction of neighboring spins. In contrast, in the plastic phase of compression, the magnetization sinks, as defects are created, increasing the disorder and typically decreasing the average atom coordination number. The effects are more pronounced in single crystals than in polycrystals, since the presence of defects in the form of grain boundaries counteracts the increase in magnetization during the elastic phase of compression. Also, the effects are more pronounced at temperatures close to the Curie temperature than at room temperature. In nanofoams, the effect of compression is minor since compression proceeds more by void reduction and filament bending—with negligible effect on magnetization—than by strain within the ligaments. These findings will prove useful for tailoring magnetization under strain by introducing plasticity.

Effect of transition metals doping in magnetic properties of Fe3Se4

We report density functional theory (DFT) study of the magnetic properties of Fe3Se4 doped with transition metals, TM (Co, Cr, Ni and Mn), where TM ions are doped in Fe sites to yield Fe2.5(TM)0.5Se4. Screening of the exchange coupling interaction and magnetization modifications were performed upon the substitution of Fe by transition metals at various Fe sites in the Fe3Se4 structure. Our study reveals that doping of Fe3Se4 with TM elements at Fe sites does not remove antiferromagnetic (AFM) coupling across layers, thus, not increasing the magnetization. This coupling is exhibited by elements with more than half-filled electron shell, i.e. Fe is such an element. Moreover, the exchange coupling between layers of Fe increases strongly as function of interlayer spacing (c lattice parameter) for both pristine and TM-doped Fe3Se4, while the magnetizations of Fe3Se4 alloys do not change significantly.

Key Role of Local Chemistry in Lattice Nitrogen‐Participated N2‐to‐NH3 Electrocatalytic Cycle over Nitrides

AbstractMetal nitrides offer great opportunities for improving activity and selectivity of electrocatalytic nitrogen reduction reaction (ENRR) via the lattice nitrogen‐participated mechanism. Understanding the role of local chemistry of lattice nitrogen is important for establishing rational design principles of nitride catalysts. Herein, high‐throughput theoretical calculations are employed to investigate lattice nitrogen‐participated ENRR over a family of antiperovskite nitrides (M′M3N, M and M′ are different metal atoms) with highly tunable surrounding environments of N atoms. The M′M3N structure comprises isolated N atoms in the center, M atoms in the first coordination shells, and M′ atoms in the second coordination shells. An appropriate M‐N bond strength is found to be crucial for designing ideal nitride catalysts. Specifically, weak M‐N bonding facilitates the participation of lattice nitrogen and better activity, but too weak M‐N bonding results in structural instability of antiperovskite. The type of M element governs M‐N bond strength through adjusting hybridization interactions between M orbital and N orbital, and the M′ element can further finely regulate M‐N bond strength via M‐M′ polarization effects. Finally, AgBa3N, AlBa3N, GaBa3N catalysts are screened to possess greater ENRR activity than the benchmarking Ru (0001) catalysts and high selectivity toward hydrogen evolution reaction.

Effect of the electrostatic field due to the surface monolayer metal atoms on the dissociation of homonuclear diatomic gases in gas-metal surface reactions

The present paper examines the role of an electrostatic field generated by the outermost monolayer of metal ions prior to gas adsorption in aiding the dissociation of homonuclear diatomic gas molecules. The interaction of five homonuclear diatomic gases, Cl2, F2, H2, N2 and O2, with several pure metals are examined using Coulomb's law to calculate the attractive and repulsive forces between the electrons or ions in the gas molecule and the free surface metallic electrons or ions assuming a Bohr model. These calculations demonstrate that the total energy of the electrostatic fields from the metals can exceed the molecular binding energies of Cl2, F2, and O2 at some distance from the metallic surface thereby suggesting that these gases interact primarily with the metallic surface in their atomic states after molecular bond dissociation prior to reaction. In contrast, H2 and N2 gases do not dissociate prior to reaching the metal surface due to the fact that the effective charge of the gas ions is less than the total electron charge at the outermost electronic shell. The present results correlate linearly with the electrochemical series standard reduction potential as well as with the Pauling electronegativity for several metals.

General oscillation strength of core–shell electron excitation by fast electrons based on Dirac solutions

General oscillation strength of core–shell electron excitation by fast electrons based on Dirac solutions

Rh19-: A high-spin super-octahedron cluster.

Probing atomic clusters with magic numbers is of supreme importance but challenging in cluster science. Pronounced stability of a metal cluster often arises from coincident geometric and electronic shell closures. However, transition metal clusters do not simply abide by this constraint. Here, we report the finding of a magic-number cluster Rh19- with prominent inertness in the sufficient gas-collision reactions. Photoelectron spectroscopy experiments and global-minimum structure search have determined the geometry of Rh19- to be a regular Oh‑[Rh@Rh12@Rh6]- with unusual high-spin electronic configuration. The distinct stability of such a strongly magnetic cluster Rh19- consisting of a nonmagnetic element is fully unveiled on the basis of its unique bonding nature and superatomic states. The 1-nanometer-sized Oh-Rh19- cluster corresponds to a fragment of the face-centered cubic lattice of bulk rhodium but with altered magnetism and electronic property. This cluster features exceptional electron-spin state isomers confirmed in photoelectron spectra and suggests potential applications in atomically precise manufacturing involving spintronics and quantum computing.