Valence Electrons Research Articles

Non-stoichimometric square sheets in RSe2−x (x ∼ 1/6) (R = Gd and Tb)

The application of optimal electron count has proven effective in predicting the existence of complex structural topologies containing electron-rich polyanionic networks, including linear and zig-zag chains, square planar structures, and simple cubic lattices of main group elements. In this study, we report the successful synthesis of a new family of magnetic compounds, RSe2−x (x ∼ 1/6) (R = Gd and Tb), using KCl flux. The resulting crystal structure of RSe2−x is tetragonal, exhibiting PbFCl-type symmetry with space group P4/nmm. Chemical composition analysis consistently reveals x ∼ 1/6, indicating chalcogen-deficient square sheets. This observation suggests that RSe2−x adheres to the 14-electron rule, as the total valence electrons per RSe2−x (x ∼ 1/6) is 14 e−. In GdSe2−x (x ∼ 1/6), the magnetic susceptibility measurement displays a lambda-shaped peak around 8 K, indicating an antiferromagnetic-type transition. However, the positive Curie–Weiss temperature (θCW) suggests the presence of an additional ferromagnetic interaction, which may result from the large magnetic moment of the Gd atoms. In contrast, TbSe2−x (x ∼ 1/6) exhibits antiferromagnetic ordering. Chemical bonding analysis also indicates that the strong Se–Se antibonding in the square net may be related to Se deficiency. Our work shed light on ellucidating the interplay between chemical rule, defects, and magnetism.

Solubility and magnetic properties of Ag−Co−Si alloy synthesized by mechanical alloying and annealing

AbstractThis present work concerns the effect of ternary addition of non‐metallic and diamagnetic silicon on the metastable solubility of the immiscible silver‐cobalt system during the course of ball milling, annealing of the ball milled samples and the corresponding magnetic properties. It should be noted that silicon has a smaller goldsmidt radius (111 pm) than silver (144 pm) and silicon+4 has more valence electrons than silver+1. Keeping the objectives of the current study in mind, silicon may thus be considered as an option for ternary addition, in contrast to metallic components. An attempt has been made to examine the phase changes that occurred in the 50 silver‐40 cobalt‐10 silicon (atom percent) system during ball milling and the subsequent isothermal annealing of the ball milled product. Phase evolution during mechanical alloying and isothermal annealing is identified by means of x‐ray diffraction, differential thermal analysis, high resolution transmission electron microscopy and magnetic measurements. The addition of silicon facilitates cobalt‘s formation of a metastable alloy with copper after 50 hours of ball milling. Annealing significantly improves the magnetic characteristics of materials that have been ball milled; the optimal combination of magnetic properties was obtained after an hour of annealing at 550 °C.

Low-Energy Magnetic States of Tb Adatom on Graphene.

Electronic structure and magnetic interactions of a Tb adatom on graphene are investigated from first principles using combination of density functional theory and multiconfigurational quantum chemistry techniques including spin-orbit coupling. We determine that the six-fold symmetry hollow site is the preferred adsorption site and we investigate electronic spectrum for different adatom oxidation states including Tb3+, Tb2+,Tb1+, and Tb0. For all charge states, the Tb 4f8configuration is retained with other adatom valence electrons being distributed over 5dxy, 5dx2+y2, and 6s/5d0single-electron orbitals. We find strong intra-site adatom exchange coupling that ensures that the 5d6sspins are parallel to the 4fspin. For Tb3+, the energy levels can be described by theJ= 6 multiplet split by the graphene crystal field. For other oxidation states, the interaction of 4felectrons with spin and orbital degrees of freedom of 6s5delectrons in the presence of spin-orbit coupling results in the low-energy spectrum composed closely lying effective multiplets that are split by the graphene crystal field. Stable magnetic moment is predicted for Tb3+and Tb2+adatoms due to uniaxial magnetic anisotropy and effective anisotropy barrier around 440 cm-1controlled by the temperature assisted quantum tunneling of magnetization through the third excited doublet. On the other hand, in-plane magnetic anisotropy is found for Tb1+and Tb0adatoms. Our results indicate that the occupation of the 6s5dorbitals can dramatically affect the magnetic anisotropy and magnetic moment stability of rare earth adatoms.

Singlet Oxygen Photocatalytic Generation by Silanized TiO2 Nanoparticles

AbstractA commercial TiO2 sample, used as received or hydrothermally treated to increase surface hydroxylation, has been functionalized by surface modification with hexadecyltrimethoxysilane. The anchoring of the silane has been characterized by means of FTIR and solid‐state NMR spectroscopies, and the grafting density was determined by thermogravimetric and N2 physisorption analyses. The silane moieties induce a partial decrease of the shielding of the valence electrons of the Ti ions at the surface, and a local modification of their crystal field, as demonstrated by XPS and UV/Vis spectroscopy, respectively. The changes in coordination and the produced oxygen vacancies result in the formation of Ti3+ defects localized in the sub‐surface region, as revealed by EPR spectroscopy. These paramagnetic centers are stabilized in the silanized samples, as the electron transfer to O2 is efficiently inhibited even under UV irradiation. However, the amount of Ti3+ centers appears to be correlated with the singlet oxygen (1O2) formation rate. Accordingly, epoxidation of limonene under UV light, chosen as a model photocatalytic reaction triggered by 1O2, occurred with higher selectivity when TiO2 was silanized and upon simultaneous NIR irradiation. These evidences suggest that in the silanized sample 1O2 may be generated through Förster‐type energy transfer from excited sub‐surface Ti3+ centers.

Theoretical study on the lattice distortion and electronic structure in the Al–Co–Cr–Fe–Ni multicomponent alloys

At present, the phase structure design for multicomponent alloys (MCAs) is mainly based on the valence electron concentration (VEC). In this work, based on the classification of valence electrons by the empirical electron theory of solid and molecule (EET), the VEC is further dissected and found that the covalent electron concentration (CEC) can be used as a criterion for determining the phase structure of MCAs. The Alx(CoCrFeNi)1-x (x = 0, 1/24, 1/12 and 1/8) alloys are designed on the basis of the CEC. The effect of Al content on the lattice distortion in the FCC phase of the alloys by combining density functional theory (DFT) and EET. The results show that the degree of lattice distortion in the FCC phase gradually increases with the increase of Al content and the interatomic bonding decreases before the phase structure transition. The alloy reaches the criticality of the phase structure transition when the Al content is 9.48 at.%.

Spin-based Atomic Periodic Model—Beyond the Periodic Table

The present article explores the potential re-arragement of all the periodic elements in terms of the spin of their valence electron, modeling them as up-spin or down-spin pointing triangles that together result in larger triangles precluding subshells, shells and the whole electron cloud (as a spin-balanced whole). Stratification of the elements according to their ratio of principal to azimuthal quantum number creates different angular cones, that not only align the elements into a compliante alternative interpretation to Mandelung’s rule, but ultimately result in a three dimensional periodic structure (that fans out and grows radially from the nucleus), resembling the shape of a flower. The model’s energetic umbrella predicts the elements Ununennium and Unbinilium. Electrical and thermal conductivities are mapped onto the new model, suggesting the existance of an instability (peak in 2D or axis in 3D) that governs the (non-) metal nature of the elements.

Valence Electron and Coordination Structure Guided Metal Active Site Design for Hydrolytic Cleavage of Carbon–Sulfide Double Bonds

Valence Electron and Coordination Structure Guided Metal Active Site Design for Hydrolytic Cleavage of Carbon–Sulfide Double Bonds

Substantially Enhanced Spin Polarization in Epitaxial CrTe2 Quantum Films.

2D van der Waals (vdW) magnets, which extend to the monolayer (ML) limit, are rapidly gaining prominence in logic applications for low-power electronics. To improve the performance of spintronic devices, such as vdW magnetic tunnel junctions, a large effective spin polarization of valence electrons is highly desired. Despite its considerable significance, direct probe of spin polarization in these 2D magnets has not been extensively explored. Here, using 2D vdW ferromagnet of CrTe2 as a prototype, the spin degrees of freedom in the thin films are directly probed using Mott polarimetry. The electronic band of 50 ML CrTe2 thin film, spanning the Brillouin zone, exhibits pronounced spin-splitting with polarization peaking at 7.9% along the out-of-plane direction. Surprisingly, atomic-layer-dependent spin-resolved measurements show a significantly enhanced spin polarization in a 3 ML CrTe2 film, achieving 23.4% polarization even in the absence of an external magnetic field. The demonstrated correlation between spin polarization and film thickness highlights the pivotal influence of perpendicular magnetic anisotropy, interlayer interactions, and itinerant behavior on these properties, as corroborated by theoretical analysis. This groundbreaking experimental verification of intrinsic effective spin polarization in CrTe2 ultrathin films marks a significant advance in establishing 2D ferromagnetic atomic layers as a promising platform for innovative vdW-based spintronic devices.

Effects of phase transition on the structure and microwave dielectric properties of (1-x)CeO2-0.5xSm2O3 (x=0-0.9) ceramics

(1-x)CeO2-0.5xSm2O3 (x=0-0.9) microwave dielectric ceramics are synthesized by the conventional solid-phase reaction method, with the effects of phase transition on structure and microwave dielectric properties being investigated in detail. The phase transition process is analyzed using the ionicity and lattice energy of (1-x)CeO2-0.5xSm2O3 ceramics, which is related to the coordination number and effective valence electron charge. With the increase of Sm3+ content, there are three phase regions: the cubic fluorite phase (0 ≤ x ≤ 0.4), the rare-earth C-type phase (0.4 <x ≤ 0.8) and the mixed phase (0.8 <x < 1.0). With the phase transition, the microstructures of (1-x)CeO2-0.5xSm2O3 (x=0-0.9) ceramics show a quasi-periodic change, where x=0.4 and x=0.8 are the critical points with similar grain size and distribution. When the phase transition occurs, the polarization, Q׃ values and the resonant frequency temperature coefficients (τƒ) of (1-x)CeO2-0.5xSm2O3 (x=0-0.8) ceramics are all mutated, which is due to the change of bond ionicity and effective valence electron charge caused by the phase transition. The microwave dielectric properties in each pure phase region vary regularly with bond ionicity and valence. Compared with the cubic fluorite phase (0 ≤ x ≤ 0.4), (1-x)CeO2-0.5xSm2O3 ceramics with rare-earth C-type phase (0.4 <x ≤ 0.8) have lower dielectric constant, with better Q׃ values and τƒ values.

Deciphering the Ce3+to Ce4+Evolution: Insight from X-ray Raman Scattering Spectroscopy at Ce N4,5Edges.

Cerium oxide, or ceria, (CeO2) is one of the most studied materials for its wide range of applications in heterogeneous catalysis and energy conversion technologies. The key feature of ceria is the remarkable oxygen storage capacity linked to the switch between Ce4+ and Ce3+ states, in turn creating oxygen vacancies. Changes in the electronic structure occur with oxygen removal from the lattice. Accordingly, the two valence electrons can be accommodated by the reduction of support cations where the electrons can be localized in empty f states of Ce4+ ions nearby.Quantifying the different oxidation states in situ is crucial to understand and model the reaction mechanism. Beside the different techniques to quantify Ce3+ and Ce4+ states, we discuss the use of X-ray Raman Scattering (XRS) spectroscopy as an alternative method. In particular, we show that XRS can observe the oxidation state changes of cerium directly in the bulk of the materials under realistic environmental conditions. The Hilbert++ code is used to simulate the XRS spectra and quantify accurately the Ce3+ and Ce4+ content. These results are compared to those obtained from in situ X-ray Diffraction (XRD) collected in parallel and the differences arising from the two different probes are discussed.

Correlations between local chemical fluctuations and grain boundary strength in Ti-Zr-Nb-Ta-Mo refractory multi-principal element alloys

Ti-Zr-Nb-Ta-Mo refractory multi-principal element alloys typically exhibit high yield strength while tensile ductility tends to be poor. In this study, we found that even after solid solution treatment of Ti-Zr-Nb-Ta-Mo alloys, significant change in ductility occur due to the local chemical fluctuations. Ta's dramatic chemical fluctuations cause variations in atomic-scale strain fields, leading to reduced grain boundary strength and brittle fracture. First-principles calculations show that (Ti, Zr)-rich at the grain boundaries increases the delocalization of valence electrons, leading to longer bond lengths and reduced crystal orbital bond index values, thereby causing grain boundary embrittlement. Our findings explore the root causes of brittleness in Ti-Zr-Nb-Ta-Mo alloys at the atomic and electronic scales, providing not only a method to analyze grain boundary embrittlement using bond length, electronic localization function and crystal orbital bond index, but also a theoretical guidance for improving the mechanical properties via grain boundary structure optimization.

"Best" Iterative Coupled-Cluster Triples Model? More Evidence for 3CC.

To follow up on the unexpectedly good performance of several coupled-cluster models with approximate inclusion of 3-body clusters [Rishi, V.; Valeev, E. F. J. Chem. Phys. 2019, 151, 064102.] we performed a more complete assessment of the 3CC method [Feller, D. . J. Chem. Phys. 2008, 129, 204105.] for accurate computational thermochemistry in the standard HEAT framework. New spin-integrated implementation of the 3CC method applicable to closed- and open-shell systems utilizes a new automated toolchain for derivation, optimization, and evaluation of operator algebra in many-body electronic structure. We found that with a double-ζ basis set the 3CC correlation energies and their atomization energy contributions are almost always more accurate (with respect to the CCSDTQ reference) than the CCSDT model as well as the standard CCSD(T) model. The mean absolute errors in cc-pVDZ {3CC, CCSDT, and CCSD(T)} electronic (per valence electron) and atomization energies relative to the CCSDTQ reference for the HEAT data set [Tajti, A. . J. Chem. Phys. 2004, 121, 11599-11613.], were {24, 70, 122} μEh/e and {0.46, 2.00, 2.58} kJ/mol, respectively. The mean absolute errors in the complete-basis-set limit {3CC, CCSDT, and CCSD(T)} atomization energies relative to the HEAT model reference, were {0.52, 2.00, and 1.07} kJ/mol, The significant and systematic reduction of the error by the 3CC method and its lower cost than CCSDT suggests it as a viable candidate for post-CCSD(T) thermochemistry applications, as well as the preferred alternative to CCSDT in general.

Research on the microstructure and properties of metastable β type Ti-8V4Mo3Cr3Zr3Al alloy with high strength and toughness

In this paper, a new type of Ti-8V-4Mo-3Cr-3Zr-3Al metastable β-type titanium alloy is designed based on alloy design parameters such as valence electron concentration (VEC), Bo, and Md, and combines them with the empirical criterion of molybdenum equivalent fractionation. Optimize the microstructure of the alloy through processes such as cold rolling, annealing, and aging treatment to obtain good mechanical properties. The microstructure of cold rolling and post rolling heat treatment was observed and analyzed using optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM), and the tensile properties of the alloy were tested. The characteristics of the alloy in terms of microstructure and properties were summarized and analyzed. The results show that the cold formability of the alloy after solid solution treatment is good, with a cold rolling reduction of over 85 %, and a large number of deformation twins generated during the cold rolling process. The yield strength after annealing and recrystallization is up to 1160 MPa, and elongation is 18.9 %. The final performance of the aged alloy is 1510 MPa for yield strength and 5 % for elongation.

Optimizing toughness in high entropy alloys using a genetic algorithm: A combined computational and experimental approach

A genetic algorithm (GA) was developed to search for high entropy alloys (HEAs) with good combinations of mechanical properties. The algorithm was designed find single-phase face-centered cubic (FCC) HEAs, already known for their ductility, with high Hall-Petch constants (K) and high critical resolved shear stresses (τY). The objective was to develop a methodology that allows the design of HEAs in a multi-objective environment, focusing on alloys that exhibit enhanced ductility and strength, achieved through an increase in its yield point without significant loss of its ultimate deformation via adjustments of K and τY values, resulting in an alloy with high toughness. The most promising alloy suggested by the genetic algorithm was an unconventional composition (Co32.73Cu15.11Fe0.72Hf0.72Mn35.97Mo3.96Ni10.43Sn0.36), with eight different elements in non-equiatomic ratios with maximized K and τY values. This alloy was then experimentally produced and characterized by scanning electron microscopy (SEM), synchrotron x-ray diffraction (XRD), transmission electron microscopy (TEM) and microhardness, with the objective of validating the predictions made by the GA. An advantage of the proposed method is the possibility of more systematically identifying and exploring new compositions in the complex composition space characteristic of these multicomponent alloys, as it directs its search towards domains that can be used to solve challenging problems involving multi-objective optimization. However, the thermodynamic parameters used for single-phase FCC prediction, namely the valence electron concentration (VEC) and the dimensionless thermodynamic parameter φ, exhibited limitations. These limitations were further explored in the present study, as evidenced by the fact that the microstructure of the selected alloy was not single-phase, which hindered the study of the mechanical properties, predicted exclusively for monophasic FCC alloys. Therefore, this work highlights the necessity for the development of novel thermodynamic equations for phase prediction, or even the integration of the genetic algorithm with other methodologies, such as CALPHAD calculations, to achieve enhanced results.

Above-threshold ionization with X-ray free-electron lasers

This study delves into the relatively uncharted territory of Above Threshold Ionization in atoms, triggered by intense X-ray radiation fields. At these frequencies, the energy of a single photon far exceeds the ionization potential of valence electrons in atoms and molecules. The conditions we examine are similar to those achievable with current or future free-electron laser facilities. Under such high-energy scenarios, the onset of strong field ionization requires a shift away from the traditional quasi-classical approach. Here, we present an analytical model to characterize how the field-free ionization potential, ponderomotive energy, and photon energy govern the transition to this regime, all accounted for by means of the Keldysh and Reiss parameters. We show that both of these parameters are needed to capture the onset of strong-field behavior due to both bound state and continuum state properties. At higher X-ray intensities, we find that ionization rates deviate from the linear intensity scaling expected from lowest order perturbative processes, corresponding to channel closure and higher-order photon absorption processes.

Ce-Doped Iron Oxide Anticorrosive Coatings: Effect of c(Ce4+):c(Fe3+) Ratio on Structure, Morphology, and Coating Anticorrosion Performance

Utilizing hydrothermal methods, Ce-doped iron oxide nanoparticles were synthesized from precursor solutions under different c(Ce4:c(Fe3+) precursor solutions. The effects of the c(Ce4+):c(Fe3+) ratio in the precursor solutions on the nanoparticle morphology and nanoparticle structure of the Ce-doped iron oxide were investigated using X-Ray diffraction, transmission electron microscopy, and scanning electron microscopy. Fourier transform infrared spectroscopy (FTIR) was used to examine the bond energy strength of the Ce-doped iron oxide nanoparticles. The electrochemical properties of the Ce-doped iron oxide nanoparticles were tested using an electrochemical workstation and a saltwater immersion resistance test. The corrosion resistance of Ce-doped iron oxide coatings at different c(Ce4+):c(Fe3+) ratios was systematically analyzed, uncovering corrosion resistance mechanisms and self-healing capabilities. The results show that as the c(Ce4+):c(Fe3+) ratio decreases, the lattice constants of the samples increase along with the average grain size. Both smaller and larger c(Ce4+):c(Fe3+) ratios are detrimental to lattice distortion in α-Fe2O3. The reduced number of valence electrons provided by cerium ions in Ce-doped iron oxide hinders the generation of holes and exerts a minor influence on the crystal band structure, leading to weaker electrochemical stability. The Ce-doped iron oxide coating prepared at a c(Ce4+):c(Fe3+) ratio of 1:60 readily generates a higher number of reactive hydroxyl radicals during corrosion, thus exhibiting enhanced self-healing capabilities and corrosion resistance.

Multireference Fock Space Coupled-Cluster Method for the (3,0) Sector.

This work reports an implementation of a novel realization of the multireference coupled cluster theory formulated in Fock space. Extending the previous formulation carried out in the (1,1) [M. Musial, R. J. Bartlett, J. Chem. Phys. 129, 044101 (2008)], (0,2) [M. Musial, R. J. Bartlett, J. Chem. Phys. 135, 044121 (2011)], and (2,0) [M. Musial, J. Chem. Phys. 136, 134111 (2012)] sectors to the (3,0) sector, we are able to treat structures with three valence electrons. The (3,0) sector describes systems with three electrons added to the reference, which means that in order to perform correlated calculations for the neutral AB molecule, we have to adopt as the reference a triply ionized structure AB3+. A desirable situation occurs when such an ion has a closed-shell structure and also dissociates into closed shell fragments. This feature makes it possible to apply the restricted Hartree-Fock scheme for the whole range of interatomic distances. Examples of molecules of this type are the diatomics formed by the atoms of alkali metals and alkaline earth metals. An analogous structure is also exhibited by alkali metal monocarbides. In the current work, we have calculated the potential energy curves and spectroscopic constants for the LiBe, LiC, and NaC molecules.

Tailoring ZrWNb-Based Refractory High Entropy Alloys: A Multidirectional Characterization Through Elemental, Physical, Thermodynamic, and Nuclear Radiation Attenuation Properties

This study explores the development and characterization of 18 novel ZrWNb[(X)(Y)] (where XY are Hf, Ta, Mo, V, Ti) refractory high entropy alloys (RHEAs) designed to enhance mechanical robustness, thermodynamic stability, and radiation shielding effectiveness. Through a rigorous analysis, we evaluated the elastic modulus, entropy, and enthalpy of mixing, atomic size difference, valence electron concentration, and the omega parameter to understand the alloys’ phase behavior and structural integrity. Our findings revealed a broad range of elastic modulus values, indicating diverse mechanical adaptability suitable for high-stress applications. The thermodynamic assessment highlighted several RHEAs with favorable phase stability, particularly ZrWNbTaHf and ZrWNbTiTaHf, which are poised for high-performance usage due to their balanced mixing entropy and enthalpy. This study also benchmarks the RHEAs against conventional alloys, with sample R1 exhibiting the lowest fast neutron effective removal cross section, underscoring its superior neutron shielding capabilities. Additionally, R1 demonstrated exceptional photon attenuation, as evidenced by its competitive half-value layer performance across an extensive energy spectrum. Collectively, these results position R1 as a standout candidate, offering a significant advancement in materials science for applications demanding stringent radiation shielding, such as in nuclear reactor environments and space exploration.

Multielectron Transfer in Halogen Batteries

AbstractMultielectron transfer in halogen batteries is a promising solution in pursuing high‐energy‐density and affordable energy storage systems. Interest in rich chemistries derived from unique valence electron structures of halogens is surging in electrode material design. However, deploying multielectron transfer chemistry comes with challenges, including limited redox reactivity and degrees of electrochemical irreversibility, which contribute to poor charging and cycling. To address these challenges, researchers explore physical/chemical strategies to activate high valence reactions and more electron transfer numbers and fix unstable valence state species through electrolyte and electrode regulation. This Concept presents the basic understanding of multielectron transfer electrochemistry concerning theoretical energy capabilities and electronic configuration evolutions. We divide multielectron transfer into two types: single and multi‐redox centers, providing an overview of the current development of multielectron transfer and hoping it will spur more intensive efforts towards a diverse energy future.

Optimizing strength-ductility synergy of the solid-solution Ti50–ZrVNbCr MEAs via coordinately adjusting VEC and lattice constant

In this study, a series of Ti50–ZrVNbCr alloys were designed under with the constant atomic radius mismatch. It was suggested that valence electron concentration (VEC) and lattice constant, which evolve oppositely in the series of the Ti50–ZrVNbCr alloys, jointly influence the mechanical properties. Based on modeling, the evolution of ductility and yield strength of the designed alloys was predicted. Ductility was predicted to be superior in the VEC range from 4.22 to 4.25, with the lattice constant correspondently ranging from 3.340 Å to 3.334 Å. The optimization of strength-ductility synergy was discussed in terms of coordinately adjusting VEC and lattice constant. The experimental results were quite consistent with the prediction results, showing that the alloy with the VEC value of 4.25 and the lattice constant of 3.334 Å, which consisted of 50 at.%Ti, 28.1 at.%Zr, 9.4 at.%V, 9.4 at.%Nb, and 3.1 at.%Cr, possessed the best ductility and superior strength-ductility synergy.