Search Results (200)

The Zeta-Minimizer Theorem provides a fully deductive variational foundation for the hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. Starting from three primitive thermodynamic axioms and the helical geometry of the phase functional, a multi-extent dynamical system is constructed that simultaneously treats the electrochemical reaction coordinates and the adsorption extents of the participating species at the solid–electrolyte interface. The combined Hessian of the phase functional yields a complete spectrum of relaxation rates whose eigenvalues and eigenvectors emerge directly from the solid blackbox constants $C_k$ and the helical partition functions of the reactive species. Adiabatic elimination of the fast surface modes produces an effective single-extent description in which voltage (or overpotential) appears as the conjugate variable, exactly analogous to the role of pressure in the corresponding gas-phase ammonia synthesis framework. The resulting nonlinear rate law is thermodynamically consistent at all conditions, recovers the Butler–Volmer and Tafel forms as well-defined limiting cases, and incorporates the effects of temperature, dilution, and catalyst-specific interface constants without empirical activation energies or adjustable reaction orders. The framework therefore unifies equilibrium, kinetics, and modal dynamics of HOR and ORR within a single variational structure, offering a parameter-light, first-principles alternative to classical empirical electrocatalytic rate expressions while preserving transparent contact with established limiting laws. Full article

In this study, the effect of Ti content on the electrochemical behavior and passive film growth mechanism of Ni₅₀Nb_50−xTi_x (x = 10, 15, and 20 at.%) metallic glasses produced via melt spinning was investigated. Structural characterization via X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the fully glassy nature and chemical homogeneity of all alloys. Electrochemical performance was evaluated in a 3.5 wt.% NaCl solution using potentiodynamic and potentiostatic polarization, as well as electrochemical impedance spectroscopy (EIS). The results showed that increasing Ti content improves corrosion resistance by reducing corrosion and passive current densities and increasing charge-transfer resistance. The Ni₅₀Nb₃₀Ti₂₀ alloy exhibited the best electrochemical performance, associated with the formation of a more stable and protective passive film. The passive film growth mechanism was analyzed using the High-Field Model (HFM). A linear relationship between inverse capacitance and anodic potential confirmed that ionic transport through the oxide layer governs passive film growth. The calculated electric field strength decreased systematically with increasing Ti content, suggesting the formation of passive films with lower defect density and enhanced barrier properties. These results demonstrate that adding Ti significantly enhances the passivation behavior of Ni-Nb metallic glasses and promotes the formation of stable oxide films with improved corrosion resistance in chloride-containing environments. Full article

Two-dimensional (2D) group-IV materials are promising for spintronics due to their silicon compatibility and tunable properties. In this work, we investigate the structural, electronic, magnetic, and optical properties of semi-hydrogenated 2D SiGe random alloys—where hydrogen atoms saturate only one side of the atomic plane—using density functional theory and many-body perturbation theory ($G{W}_0$). Substitutional disorder is modeled via representative high-symmetry configurations introduced by Baldereschi and co-workers to enable quasiparticle and optical simulations in large supercells. We demonstrate that these semi-hydrogenated alloys possess an intrinsic magnetic semiconducting ground state, arising from the electronic structure of the system, with an integer magnetic moment of $1{\mathsf{\mu }}_{\mathrm{B}}$ per primitive cell. The spin-resolved electronic structure features nearly flat frontier bands and a finite energy gap, which is significantly renormalized by quasiparticle corrections while maintaining robust spin polarization. These properties remain remarkably stable across different realizations of chemical disorder and over a wide range of alloy compositions considered in this work. Optical spectra calculated within the random phase approximation reveal a composition-dependent red-shift of the low-energy onset in the imaginary part of the dielectric function, consistent with the evolution of the quasiparticle electronic structure and the persistence of flat spin-polarized frontier bands. Our findings establish semi-hydrogenated 2D SiGe random alloys as a resilient model platform to explore interaction-driven magnetism in disordered two-dimensional systems, while simultaneously offering realistic prospects for spintronic and magneto-optoelectronic applications in the presence of chemical disorder. Full article

In this work, the structural, electronic, charge-transfer, thermal, and magnetic properties of pristine and Fe-doped silicon carbide nanosheets (SiCNShs) were systematically investigated using spin-polarized density functional theory (DFT) within the Local Spin Density Approximation including Hubbard correction (LSDA + U). A 4 × 4 SiCNSh supercell containing 80 atoms was considered, where Fe atoms were substitutionally introduced at carbon sites to evaluate dopant-induced modifications in the nanosheet. Structural optimization, energy convergence, force minimization, and stress evolution analyses confirm that Fe incorporation preserves the structural integrity of the SiCNSh and leads to energetically stable configurations. The calculated defect formation energy (−7.44 eV/atom) demonstrates the thermodynamic feasibility of Fe substitution, while ab initio molecular dynamics (AIMD) simulations at 300 K verify the thermal stability of the energetically favorable Fe-doped configuration. Electronic-structure calculations reveal that pristine SiCNSh exhibits a nonmagnetic semiconducting nature with a band gap of approximately 2.4 eV, whereas Fe incorporation significantly modifies the electronic structure through pronounced Fe–3d/C–2p/Si–3p orbital hybridization. The band gap is reduced to approximately 1.1 eV for the single-Fe-doped system and further decreases to 0.53/0.51 eV (spin-up/spin-down) in the double-Fe configuration, while preserving semiconducting behavior. Spin-polarized band structure and density of states analyses demonstrate clear spin asymmetry near the Fermi level, indicating strong dopant-induced spin polarization and exchange interactions. Charge-density difference and Bader charge analyses reveal substantial dopant-induced charge redistribution characterized by electron depletion around Fe atoms, enhanced electron accumulation on neighboring carbon atoms, and partial charge neutralization of nearby Si atoms, resulting in a more localized covalent Si–C–Fe bonding environment. Mulliken spin population analysis further demonstrates robust ferromagnetic ordering, where the Fe dopant acts as the dominant magnetic center with strong induced spin polarization extending into neighboring Si and C atoms. Comparison between ferromagnetic (FM) and antiferromagnetic (AFM) configurations confirms that the 2Fe@C-doped SiCNSh stabilizes in a ferromagnetic ground state, exhibiting a favorable FM–AFM energy difference of 0.216 eV. Based on the mean-field approximation, the Curie temperature was estimated to be approximately 837 K, indicating strong magnetic stability significantly above room temperature. The present findings collectively demonstrate that Fe incorporation effectively tailors the electronic and magnetic properties of SiCNSh through band-gap engineering, spin-symmetry breaking, and stabilization of high-temperature ferromagnetism. These combined characteristics establish Fe-doped SiCNShs as promising candidates for spintronic devices, magnetic semiconductors, spin injectors, spin filters, and non-volatile magnetic memory applications. Full article

The segregation of niobium (Nb) at the FeΣ3(111) grain boundary and its influence on interfacial cohesion were investigated via spin-polarized density functional theory calculations. Nb atoms exhibit strong site-selective segregation, with Site 1 being the most thermodynamically favorable one (segregation energy of −2.47 eV), owing to its largest local Voronoi volume. Electronic structure analyses reveal pronounced Nb-4d/Fe-3d orbital hybridization and localized charge accumulation between Nb and neighboring Fe atoms, enhancing covalent bonding at the boundary. First-principles tensile simulations show that single-Nb segregation increases the critical strain from 13.58% to 15.76% and the theoretical tensile strength from 16.32 GPa to 19.64 GPa. However, double-Nb segregation reduces the work of separation to 3.26–4.24 J/m², revealing a competition between segregation strengthening and solute-induced weakening that implies an optimal Nb concentration window for grain boundary engineering. Full article

The study presents a comprehensive first-principles investigation of the structural, electronic, and magnetic properties of rocksalt scandium nitride (ScN) and its Cr- and Mn-doped derivatives using spin-polarized density-functional theory within the GGA + U (U_Cr = 3.5 eV, U_Mn = 2.7 eV) and HSE06 frameworks. Pristine ScN crystallizes in the cubic Fm$\bar{3}$m structure and exhibits narrow-gap semiconducting behavior, with an indirect band gap of 0.82 eV obtained from hybrid-functional calculations, in excellent agreement with reported theoretical values. Substitutional doping with Cr and Mn introduces localized 3d states near the Fermi level, driving a transition toward spin-polarized metallic or half-metallic behavior accompanied by robust ferromagnetism. Density-of-states and band-structure analyses reveal that magnetism and charge transport in the doped systems are dominated by exchange-split transition-metal 3d states hybridized with N-2p orbitals. Total energy calculations confirm ferromagnetic ground states for both Cr- and Mn-doped ScN, with Mn substitution yielding stronger exchange stabilization and higher magnetic moments. Magnetocrystalline anisotropy energies, evaluated using the force-theorem approach, are found to be negligibly small, indicating weak anisotropy consistent with the moderate spin–orbit coupling strength in ScN-based nitrides. Nevertheless, symmetry breaking around dopant sites gives rise to a finite Dzyaloshinskii–Moriya interaction, leading to weak spin canting and non-collinear magnetic tendencies. The interplay between magnetic exchange coupling, spin–orbit interaction, and local inversion symmetry breaking positions of Cr- and Mn-doped ScN as promising dilute magnetic semiconductors with tunable spin polarization and chiral magnetic interactions, offering a viable platform for nitride-based spintronic and magneto-electronic applications. Full article

Developing sensitive and reversible CO sensors requires precise control of material–analyte interactions. Using DFT, we investigate CO sensing on bimetallic (Fe, Pt) anchored on N-doped graphene (TM₂–N₄–C), focusing on active-site density effects. Three densities are considered: low (12.7 Å), medium (8.5 Å), and high (4.2 Å). FePt–N₄–C band gaps exhibit non-monotonic tuning, approaching metallicity at high density. CO chemisorbs on Fe sites, but physisorbs on Pt sites. FePt exhibits stronger synergistic adsorption than homonuclear counterparts. While adsorption generally strengthens with density, spin-polarized calculations qualitatively reorder this trend via spin delocalization. High temperatures drastically improve recovery; low-density FePt–N₄–C reaches 65 s at 498 K. Three design principles emerge: low-density heteronuclear systems for reversible sensing, medium-density high-spin states for ultra-sensitive capture, and high-density configurations for work function sensors. This work establishes active site density as a key electronic and kinetic knob for graphene-based CO sensors. Full article

In this work, a comprehensive first-principles investigation of the electronic, magnetic, and optical properties of pristine and Fe-, Co-, and Ni-doped MoS₂ monolayers is presented within the framework of density functional theory. Substitutional transition-metal doping at the Mo site is shown to induce spin-polarized impurity states within the pristine band gap, leading to significant modifications of the electronic structure, including metallic, semimetallic, or half-metallic behavior depending on the dopant species. The calculated spin-resolved band structures and projected density of states reveal a strong hybridization between the dopant $3d$ orbitals and the Mo-$4d$/S-$3p$ states, giving rise to sizable magnetic moments and dopant-dependent exchange splitting. When spin–orbit coupling is included, the combined effect of exchange interactions and relativistic effects leads to an effective valley splitting at the K and $K^{\prime }$ points, whose magnitude and sign depend sensitively on the chemical nature of the dopant. Optical properties are analyzed within a linear-response framework, showing pronounced dopant-induced modifications of the optical spectra. While the pristine monolayer exhibits well-defined excitonic features, transition-metal substitution introduces low-energy optical transitions associated with impurity-related states. Consequently, the exciton binding energies estimated from the difference between the electronic and optical gaps are interpreted as effective measures of dopant-induced perturbations to optical transitions, rather than as quantitative many-body excitonic binding energies in the strict sense. These results provide microscopic insight into the interplay between magnetism, spin–orbit coupling, and optical response in doped MoS₂ monolayers, highlighting the potential of transition-metal substitution as a route to engineer spin- and valley-dependent phenomena in two-dimensional materials. Full article

Interlayer-sliding ferroelectricity in van der Waals bilayers enables ultralow-power switching, but practical devices are often limited by contact/interface scattering and weak coupling between polarization and transport. We propose homophase lateral architectures based on bilayer Janus MoSSe: a 1T/2H/1T ferroelectric tunnel homojunction and an H-phase lateral p–i–n photodetector (artificially doped electrode). Metallic 1T electrodes largely eliminate contact barriers and maximize polarization-driven tunneling modulation. Using non-equilibrium Green’s function–density functional theory (Perdew–Burke–Ernzerhof approximation, without explicit spin–orbit coupling), we find that AB to BA sliding reduces the current from the nA range to the pA range, with the minimum current of|I_OFF|_min = 2.83 pA, yielding giant tunneling electroresistance up to 5.3 × 10⁴%. Projected local density of states reveals a non-rigid long-range potential redistribution that reshapes the tunneling barrier and opens high-transmission channels. In the p–i–n photodetector, the response is strongly anisotropic and stacking-dependent: AB reaches photocurrent density J_ph ≈ 7.2 µA·mm⁻² at 2.6 eV for in-plane light versus ≈ 2.9 µA·mm⁻² at 3.5 eV for out-of-plane, and exceeds BA by 1.5–1.8 times due to density of states advantages and Mo-d orbital selection rules. Bilayer Janus MoSSe therefore provides a reconfigurable platform for high-contrast memory and polarization-sensitive photodetection. Full article

As the process node is scaled down, the spin-transfer-torque magnetic random-access memory (STT-MRAM) exhibits higher memory density than the static random-access memory (SRAM), making it one of the more promising successors of the low-level on-chip cache memory. However, the low read margin (RM) of the magnetic tunnel junction (MTJ) in STT-MRAM can limit the achievable read accuracy. We implemented 2-bit channel quantization for error-correcting code (ECC) schemes and explored the trade-offs between improved read accuracy and factors such as circuit area, power consumption, and latency. The proposed quantization scheme consists of a sensing amplifier-based 2-bit quantizer and MTJ resistor-based soft-decision thresholds. Compared to 1-bit channel quantization using the Bose–Chaudhuri–Hocquenghem (BCH) code, the proposed 2-bit quantization architecture achieves a fourfold reduction in frame error rate (FER) from $8.0\times {10}^{-4}$ to $2.0\times {10}^{-4}$ when paired with polar codes and successive cancellation (SC) decoding. Additionally, this approach results in decoding complexity that is only 1/13th of that required for BCH at a 0.7 code rate. Full article

Metal-free two-dimensional (2D) polymers built from open-shell π-conjugated units offer a promising platform for realizing correlation-driven magnetism without transition metal elements. Here, we present a systematic first-principles study of phenalenyl-based 2D polymers that elucidates how atomic-level chemical substitution controls magnetic order through the interplay of electronic correlation and sublattice symmetry. Combining density functional theory with an effective tight-binding and Hubbard model analysis, we show that atomic substitution with boron or nitrogen on phenalenyl building blocks acts as a sublattice-resolved tuning knob for both the ratio of on-site Coulomb interaction to inter-site hopping (U/t) and the relative on-site energies of the two sublattices. Sublattice-asymmetric substitution with boron or nitrogen breaks sublattice equivalence and drives the system from an antiferromagnetic Mott-insulating state into spin-polarized semiconducting phases with pronounced spin-dependent gaps. In contrast, uniform substitution on both sublattices preserves symmetry and yields nonmagnetic metallic states characterized by rigid band shifts rather than correlation-driven spin polarization. These results establish a unified microscopic framework in which electronic correlations and sublattice symmetry emerge as cooperative yet independently tunable parameters, providing general design principles for metal-free 2D π-conjugated materials with tailored magnetic and spintronic functionalities. Full article

Two-dimensional magnetic materials with weak spin-orbit coupling would endow them with great potential for applications in low-power spintronic logic devices. In this work, the stability and magnetism of nonmetal (N, O, F, P) doped 1T-ZrS₂ monolayers is systematically studied by using first principles calculations based on density functional theory. Pristine ZrS₂ monolayer is a nonmagnetic semiconductor with an indirect band gap of 1.15 eV. Among the configurations of nonmetal-atom adsorption, substitutional doping, and vacancy defects, fluorine adsorption on the ZrS₂ monolayer is regarded as an optimal doping strategy. At the concentration of 11.11% in F-adsorbed ZrS₂, the spontaneous magnetization of F-adsorbed ZrS₂ monolayer occurs at the ground state with the stable magnetic states; the magnetic moments are about 0.674 μ_B, which mainly originates from the hybridization between the p-orbitals of S atoms and F atoms (0.315 μ_B) and d-orbitals of Zr atoms (0.323 μ_B). Moreover, the F-adsorbed ZrS₂ monolayer under 0–4% strain delivers consistently low spin polarization energy with stable p-d hybridization, offering their promising potential for their practical applications in low-power spintronic devices. Full article

Intermetallic alloys based on A15-type compounds, including cubic Ti₃Sb, attract increasing interest due to their tunable electronic properties and potential for surface-related functional applications. Here, the interaction of nitrogen with Ti₃Sb is systematically investigated using spin-polarized density functional theory within the GGA-PBE approximation. Nitrogen adsorption was analyzed on the Ti₃Sb (111), (100), and (110) surfaces by considering top, bridge, and hollow sites at different surface coverages. Low nitrogen coverage was found to minimize lateral adsorbate interactions, allowing reliable evaluation of single-atom adsorption energies. Among the studied configurations, nitrogen adsorption at the hollow site of the Ti₃Sb (111) surface is energetically most favorable. In addition, partial substitution of Ti or Sb atoms by nitrogen in Ti₃Sb supercells was examined to assess its effect on bulk electronic properties. Nitrogen incorporation leads to pronounced modifications of the electronic band structure, density of states, and local magnetic moments, with a strong dependence on crystallographic direction. The calculated results reveal distinct electronic anisotropies originating from direction-dependent band dispersion and associated effective carrier masses. These findings clarify the role of nitrogen in tailoring both surface and bulk electronic characteristics of Ti₃Sb and provide a theoretical basis for the targeted design of A15-type intermetallic materials for sensing, catalytic, and energy-related applications. Full article

Spin angular momentum is a fundamental dynamical property of elementary particles and fields, playing a critical role in light–matter interactions. In optical studies, the optical spin angular momentum is closely linked to circular polarization. Research on the interaction between optical spin and matter or structures has led to numerous novel optical phenomena and applications, giving rise to the emerging field of spin optics. Historically, researchers primarily focused on longitudinal optical spin aligned parallel to the mean wavevector. In recent years, investigations into the spin–orbit coupling properties of confined fields—such as focused beams, guided waves, and evanescent waves—have revealed a new class of optical spin oriented perpendicular to the mean wavevector, referred to as optical transverse spin. In the optical near-field, such transverse spins arise from spatial variations in the momentum density of confined electromagnetic waves, where strong coupling between spin and orbital angular momenta leads to various topological spin structures and properties. Several reviews on optical transverse spin have been published in recent years, systematically introducing its fundamental concepts and the configurations that generate it. In this review, we detail recent advances in spin optics from three perspectives: theory, experimental techniques, and applications, with a particular emphasis on the fundamental physics of transverse spin and the resulting topological structures and characteristics. The conceptual and theoretical framework of spin optics is expected to significantly support further exploration of optical spin-based applications in fields such as optics imaging, topological photonics, metrology, and quantum technologies. Furthermore, these principles can be extended to general classical wave systems, including fluidic, acoustic, and gravitational waves. Full article

The first-principles method using density functional theory (DFT) reveals the mechanics, electronic structure, and magnetic properties of six Zr-based equiatomic quaternary Heusler compounds and their transformation under hydrostatic pressure. The results show that these compounds maintain mechanical stability under hydrostatic pressures of 0–100 GPa, and the ductility of all the alloys is improved except ZrCrFeGe. In the ground state structure, ZrVFeAl and ZrCrFeGe are half metals, ZrVCoAl and ZrCrFeAl are spin gapless semiconductors, while ZrCrMnAl and ZrMnFeAl are regarded as nearly half metals. ZrVFeAl, ZrVCoAl, ZrCrFeAl, and ZrCrFeGe have high spin polarization and satisfy the Slater–Pauling rule, and their spin-flip band gaps are 0.43 eV, 0.35 eV, 0.14 eV, and 0.11 eV, respectively. These half-metallic compounds maintain half-metallicity within a certain pressure range, while spin gapless semiconductors (SGS) complete the SGS~half-metal~near-half-metal transition under hydrostatic pressure. These half-metallic compounds and spin gapless semiconductors are ideal candidates for spintronic applications. Full article