Search Results (262)

A first-principles investigation was conducted to characterize the novel Cr₂ZnC MAX phase and its exfoliated MXene nanosheet, Cr₂C. The study critically examines the effect of electron correlations on the bulk phase, revealing that the PBE+U framework, unlike standard PBE, yields a dramatically enhanced magnetic moment of 12.80 μ_B (vs. 1.88 μ_B), confirming the necessity of this approach for Cr-based carbides. The phase stability is confirmed through rigorous analysis of its thermodynamic, dynamic, and mechanical properties. For the derived 2D Cr₂C, results confirm a robust half-metallic state with a total magnetic moment of 8.00 μ_B, characterized by a metallic spin-majority channel and a semiconducting spin-minority channel with a 2.41 eV direct gap, leading to near-ideal spin polarization. These combined features establish Cr₂C as a highly promising candidate for next-generation spintronic applications and 2D magnetic devices requiring room-temperature stability. Full article

The composite material MgH₂-EEWNi-Cr (20 wt. %) with a hydrogen content of 5.2 ± 0.1 wt.% is characterized by improved hydrogen interaction properties compared to the original MgH₂. The dissociation of the material occurs in three temperature ranges (86–117, 152–162, and 281–351 °C), associated with a complex of effects consisting of changes in the specific surface area of the material, alterations in the crystal lattice during ball milling, and changes in the electronic structure in the presence of a Ni–Cr catalyst, based on first-principles calculations. The decrease in desorption activation energy (E_d = 65–96 ± 1 kJ/mol, ΔE_d = 59–90 kJ/mol) is due to the catalytic effect of N–Cr, leading to a faster decomposition of the hydride phase. Based on the results of ab initio calculations, Ni–Cr on the MgH₂ surface leads to a significant decrease in hydrogen binding energy (ΔE_b = 60%) compared to pure magnesium hydride due to the formation of Ni–H and Cr–H covalent bonds, which reduces the degree of H–Mg ionic bonding. The results obtained allow us to expand our understanding of the mechanisms of hydrogen interaction with storage materials and the possibility of using these as mobile hydrogen storage and transportation materials. Full article

In ultrafast science, the strong-field approximation (SFA) provides a powerful framework to describe high-order harmonic generation (HHG) and related phenomena. Meanwhile, within the current ab initio theoretical framework, the use of nonlocal potentials in calculating multi-electron molecular wave functions is almost unavoidable. We find that when such wave functions are directly applied to compute transition dipole moments for correcting SFA, it introduces a fundamental gauge transformation problem. Specifically, the nonlocal potential contributes an additional gauge-dependent phase function to the dipole operator, which directly modifies the phase of the transition dipole. As a consequence, the saddle-point equations acquire an entirely different structure compared to the standard SFA, leading to a splitting of the conventional short and long classical trajectories in HHG into multiple distinct quantum trajectories. Here, “complex molecules” refers to multi-center molecular systems whose nonlocal electronic structure leads to gauge-dependent strong-field responses. Our analysis highlights that the validity of gauge in-variation cannot be assumed universally in SFA framework. Our approach combines the molecular strong-field approximation with gauge transformation analysis, incorporating nonlocal pseudopotentials, saddle-point equations, and multi-center recombination effects. Full article

We present a time-dependent nonperturbative theory of the reconstruction of attosecond beating by interference of multiphoton transitions (RABBIT) for photoelectron emission from hydrogen atoms in the transverse direction relative to the laser polarization axis. Extending our recent semiclassical strong-field approximation (SFA) model developed for parallel emission, we deduce analytical expressions for the transition amplitudes and demonstrate that the photoelectron probability distribution can be factorized into interhalf- and intrahalfcycle interference contributions, the latter modulating the intercycle pattern responsible for sideband formation. We identify the intrahalfcycle interference arising from trajectories released within the same half cycle as the mechanism governing attosecond phase delays in the perpendicular geometry. Our results reveal the suppression of even-order sidebands due to destructive interhalfcycle interference, leading to a characteristic spacing between adjacent peaks that doubles the standard spacing observed along the polarization axis. Comparisons with numerical calculations of the SFA and the ab initio solution of the time-dependent Schrödinger equation confirm the accuracy of the semiclassical description. This work provides a unified framework for understanding quantum interferences in attosecond chronoscopy, bridging the cases of parallel and perpendicular electron emission in RABBIT-like protocols. Full article

Aluminum/lithium (Al/Li) alloy is a promising energetic material for solid composite propellants. The bonding structure, topological shape, density, cohesive energy, and mechanical and diffusion properties of the Al/Li alloy bulks and oxidation shells are calculated systematically using the large-scale force-field molecular dynamics simulations together with the ab initio quantum chemistry calculations. Theoretical predicted structures and dynamic properties for various crystalline and amorphous reference compounds are compared with the available experimental data to validate the force-field simulations. The dependence of the structures and properties on the Li contents ranging from 2 to 50 wt% is clarified. It is revealed that both Al and Li atoms are resident in the same Al or Li environment in the Al/Li alloys. The presence of the crystalline δ’-Al₃Li and β-AlLi phases in the Al/Li alloys is rationalized in terms of the coordination of Al/Li and the thermodynamic free energy of Li substitution. A homogenous six-coordinated Al/Li alloy could be generated with a Li content of 20 wt%. Young’s moduli of the alloys are improved via the low Li addition due to the anisotropic effect. The Al/Li/O oxidation shell is less dense than the amorphous alumina but the densities of oxides are generally higher than those of the corresponding Al/Li alloys. As the Li content increases, the Al/Li/O oxides form the ordered four-coordinated AlO₄ passages together with the under-coordinated Li-O units, leading to considerably deteriorated mechanical performance and efficient Li diffusion with an activation energy of about 20 kJ/mol. The present work provides a deep understanding of the Al/Li alloys and Al/Li/O oxides in terms of performance and exposure stability. Full article

Materials with high hardness are critical for industrial and aerospace applications, prompting the search for novel compounds with robust covalent networks. Using a first-principles structure prediction method, we systematically explored the phase stability of Si–N compounds under high pressure. We identified two thermodynamically stable phases: Si₆N with P-1 symmetry and SiN₄ with space group R-3c. Phonon spectra and ab initio molecular dynamics simulations confirm the dynamical and thermal stability of R-3c SiN₄ at ambient pressure and up to 2000 K. Notably, R-3c SiN₄ exhibits exceptional mechanical properties with a Vickers hardness of 31 GPa, a bulk modulus of 259.53 GPa, and a Young’s modulus of 485.38 GPa. Furthermore, SiN₄ possesses a high energy density (1.1 kJ·g⁻¹) and outstanding detonation pressure and velocity (228 kbar, 7.11 km·s⁻¹), both exceeding those of TNT, making it a potential high-energy-density materials. In addition, electronic structure analysis reveals SiN₄ has a band gap of 2.5 eV, confirming its nonmetallic characteristics and strongly covalent nature. These findings provide theoretical guidance for the future synthesis of Si–N phases and establish a foundation for designing novel materials that combine high hardness with high-energy density performance. Full article

In this study, the sublimation and vapor pressure characteristics of RuO₄ were systematically investigated using ab initio thermodynamic calculations. Structural optimizations and vibrational frequency analyses were performed for gaseous RuO₄ and four candidate solid phases (monoclinic Cm, P2₁/c, C2/c, and cubic P-43n) within the density functional theory (DFT) framework. Gibbs free energies were evaluated by incorporating electronic energies, zero-point corrections, and entropic contributions from translational, rotational, and vibrational modes. The results identify monoclinic C2/c and cubic P-43n as the most stable solid phases across the studied temperature range. Calculated sublimation temperatures of 322 K at 1 atm and 240 K at 1 × 10⁻³ atm were obtained in good agreement with experimental melting and boiling points. Calculated vapor pressures show reasonable agreement with experimental measurements below the triple point, with deviations at higher temperatures attributable to approximating liquid-gas behavior using solid-gas sublimation data. These findings provide the first theoretical description of RuO₄ vapor pressure and offer a computational framework extendable to other transition-metal ALD precursors. Full article

In this study, we employ a Support Vector Machine (SVM) model to efficiently classify the phases of thermoelectric (TE) alloys. While ab initio calculations and experiments have explored the phases of functional TE materials, the large variety of alloys makes these explorations time-consuming and expensive. Therefore, there is a critical need for time-efficient methods to accelerate the discovery and development of new TE materials. Recently, machine learning (ML) classification models have been applied to predict material phases, including those of multi-principal element alloys. Using an SVM to classify phases of TE alloys, our results demonstrate that the model achieves prediction accuracies ranging from $77\%$ to $92\%$. Additionally, cross-validation across various TE phases is performed to demonstrate the model’s robustness in phase differentiation. This work offers a time-efficient computational approach to distinguish TE material phases, offering valuable insights that can aid in the evaluation and design of high-performance thermoelectric materials. Full article

NaNbO₃ (NN), known for the complexity of its phase transition sequence, is antiferroelectric (AFE) at room temperature, while both LiNbO₃ (LN) and KNbO₃ (KN) are ferroelectric (FE). The origin of ferroelectricity in ABO₃ perovskites is believed to lie in the B-O hybridization, but the origin of antiferroelectricity remains unclear. Recent ab initio studies have shown that the same B-O hybridization is necessary in AFE and proposed an additional, anharmonic contribution to the potential of the A-site atom as the crucial difference between FE and AFE perovskites. We used structure factors obtained from X-ray diffraction experiments in combination with the Maximum Entropy Method to obtain electron densities for LN, KN, and NN and identify differences in their bonding behavior. We present experimental evidence for anharmonic A-site contributions of varying strength in alkali niobates, pointing at a new path for the design of (anti-)ferroelectric materials. Full article

Tungsten disulfide (WS₂), a two-dimensional layered material with favorable electronic properties, has been explored as a promising negative electrode material for calcium-ion batteries (CIBs). Despite its use in monovalent systems, its performance in divalent Ca²⁺ intercalation remains poorly understood. Herein, a combined theoretical and experimental framework is used to elucidate the electronic mechanisms underlying Ca²⁺ intercalation. Theoretical insights were obtained through density functional theory calculations, incorporating periodic simulations using the Vienna Ab initio Simulation Package, and localized orbital-level analysis using the discrete variational Xα method. These approaches reveal that Ca²⁺ insertion induces significant interlayer expansion, lowers diffusion barriers, and narrows the bandgap compared to Li⁺. Orbital analysis revealed strengthened W–S bonding and diminished antibonding interactions, which may contribute to the improved structural resilience. Electrochemical tests validated these predictions; the CaWS₂ electrode delivered an initial discharge capacity of 208 mAh·g⁻¹ at 0.1C, with 61% retention after 50 cycles at 1C. The voltage profile exhibits a distinct plateau near 0.7 V, consistent with a two-phase-like intercalation mechanism, contrasting with the gradual slope observed for Li⁺. These findings suggest that Ca²⁺ intercalation facilitates both rapid ion transport and enhanced structural robustness. This study offers mechanistic insights into multivalent-ion storage and supports the design of high-performance CIB electrodes. Full article

The MA₂Z₄ family represents a class of two-dimensional materials renowned for their outstanding mechanical properties and excellent environmental stability. By means of elemental substitution, we designed two novel phases of ScSi₂N₄, namely β₁ and β₂. Their dynamical, thermal, and mechanical stabilities were thoroughly verified through phonon dispersion analysis, ab initio molecular dynamics (AIMD) simulations, and calculations of mechanical parameters such as Young’s modulus and Poisson’s ratio. Electronic structure analysis using both PBE and HSE06 methods further revealed that both the β₁ and β₂ phases exhibit metallic behavior, highlighting their potential for battery-related applications. Based on these outstanding properties, the climbing image nudged elastic band (CI-NEB) method was employed to investigate the diffusion behavior of Li, Na, and K ions on the material surfaces. Both structures demonstrate extremely low diffusion energy barriers (Li: 0.38 eV, Na: 0.22 eV, K: 0.12 eV), indicating rapid ion migration—especially for K—and excellent rate performance. The lowest barrier for K ions (0.12 eV) suggests the fastest diffusion kinetics, making it particularly suitable for high-power potassium-ion batteries. The significantly lower barrier for Na ions (0.22 eV) compared with Li (0.38 eV) implies that both β₁ and β₂ phases may be more favorable for fast-charging/discharging sodium-ion battery applications. First-principles calculations were applied to determine the open-circuit voltage (OCV) of the battery materials. The β₂ phase exhibits a higher OCV in Li/Na systems, while the β₁ phase shows more prominent voltage for K. The results demonstrate that both phases possess high theoretical capacities and suitable OCVs. Full article

The paradigm of molecular-network conformations in Se-rich glassy arsenoselenides As_xSe_100−x compositionally approaching pure Se (x < 10) is considered, employing comprehensive XRD analysis of diffuse peak-halos and nanocrystalline reflections from the known Se polymorphs in their XRD patterns. Within a modified microcrystalline model, the changes with growing Se content in these alloys are interpreted in terms of suppression in intermediate range ordering due to shifting to high diffraction angles and a narrowed FSDP (first sharp diffraction peak)-related diffuse peak-halo, accompanied by enhancement in extended range ordering due to a shift to low diffraction angles and a broadened SSDP (second sharp diffraction peak)-related peak-halo. Overlapping of these peak-halos is enhanced in Se-rich alloys, tending towards unified FSDP-SSDP-related halos with characteristic doublet asymmetry due to the remnants of nanocrystalline trigonal t-Se. Drastic enhancement of the crystallization processes related to the trigonal t-Se phase is a principal feature of nanostructurization effects in Se-rich glassy arsenoselenides driven by nanomilling. The nanostructurization response in these alloys is revealed as a fragmentation impact on the correlation length of the FSDP-responsible entities, accompanied by an agglomeration impact on the correlation length of the SSDP-responsible entities. The FSDP- and SSDP-related diffuse peak-halos become more distinguishable in the XRD patterning of nanostructured arsenoselenides, being associated with other contributions from crystalline remnants, such as those expected in transition to glassy arsenoselenides with higher Se content. An irregular sequence of randomly distributed cis- and trans-configurated multiatomic Se linkages is visualized by ab initio quantum-chemical modeling of Se_n chain- and ring-like conformations. The most critical point of molecular-network disproportionality analysis in the examined arsenoselenide As_xSe_100−x glassy alloys obeying the chain-crossing model corresponds to x = 7 (equivalent to 93 at. % of Se in the binary As-Se system), as an equilibrium point between mixed cis-trans-configurated Se₇ chains and exceptionally cis-configurated molecular Se₈ rings. At the basis of developed models, the paradigm of thermodynamically stable molecular-network conformations in the nanostructured Se-rich arsenoselenides As_xSe_100−x (x < 10) is surely resolved in favor of chain-like network-forming conformations composed of mixed cis-trans-configurated network-forming multiatomic Se fragments. Full article

The development of high-performance solid electrolytes is critical to advancing solid-state lithium-ion batteries (SSBs), with lithium lanthanum zirconium oxide (LLZO) emerging as a leading candidate due to its chemical stability and wide electrochemical window. In this study, we systematically investigated the effects of cation dopants, including aluminum (Al³⁺), tantalum (Ta⁵⁺), gallium (Ga³⁺), and rubidium (Rb⁺), on the structural, electronic, and ionic transport properties of LLZO using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. It appeared that, among all simulated results, Al-LLZO exhibits the highest ionic conductivity of 1.439 × 10⁻² S/cm with reduced activation energy of 0.138 eV, driven by enhanced lithium vacancy concentrations and preserved cubic-phase stability. Ta-LLZO follows, with a conductivity of 7.12 × 10⁻³ S/cm, while Ga-LLZO and Rb-LLZO provide moderate conductivity of 3.73 × 10⁻³ S/cm and 3.32 × 10⁻³ S/cm, respectively. Charge density analysis reveals that Al and Ta dopants facilitate smoother lithium-ion migration by minimizing electrostatic barriers. Furthermore, Al-LLZO demonstrates low electronic conductivity (1.72 × 10⁻⁸ S/cm) and favorable binding energy, mitigating dendrite formation risks. Comparative evaluations of radial distribution functions (RDFs) and XRD patterns confirm the structural integrity of doped systems. Overall, Al emerges as the most effective and economically viable dopant, optimizing LLZO for scalable, durable, and high-conductivity solid-state batteries. Full article

Molecular dynamics (MD) simulations have been performed on the energetics, mechanical properties, and irradiation response of seventy-three 3C-SiC symmetric tilt grain boundaries (STGBs) with three tilt axes (<100>, <110> and <111>). The effect of GB characteristics on the STGB properties has been investigated. The GB energy is positively and linearly correlated with the excess volume, but the linearity in SiC is not as good as in metals, which stems from the inhomogeneous structural relaxation near GBs induced by orientation-sensitive covalent bonding. For <110>STGBs, the shear strength exhibits symmetry with respect to the misorientation angle of 90°, which is consistent with ab initio calculations for Al in similar shear orientations. Cascades are performed with 8 keV silicon as the primary knock-on atom (PKA). No direct correlation is found between the sink efficiency of GBs for defects and GB characteristics, which comes from the complexity of the diatomic system during the recovery phase. For GBs with smaller values of Σ, the GBs exhibit a weaker blocking effect on the penetration of irradiated defects, resulting in a lower number of defects in GBs and a higher number of total surviving defects. In particular, it is seen that the percentage decrease in tensile strength after irradiation is positively correlated with the Σ value. Taken together, these results help to elucidate the impact of GB behavior on the mechanical properties of as well as the primary irradiation damage in SiC and provide a reference for creating improved materials through GB engineering. Full article

Vibrational analysis of peptides in solution and the theoretical determination of the effects of the microenvironment on infrared and Raman spectra are of key importance in many fields of chemical interest. In this work, we present a computational study combining static quantum mechanical calculations with ab initio molecular dynamics simulations to investigate the vibrational behavior of three peptide models in both the gas phase and in explicit water, under non-periodic boundary conditions. The vibrational spectra of the main amide bands, namely amide I-III and A, were analyzed using a time–frequency approach based on the wavelet transform, which allows the resolution of transient frequency shifts and mode couplings along the trajectories. This combined approach enabled us to perform a time-resolved vibrational analysis revealing how vibrational frequencies, especially of the C=O and N–H stretching modes, evolve over time due to dynamical microsolvation. These fluctuations modulate vibrational couplings and lead to spectral broadening and frequency shifts that correlate with the local structuring of the solvent. In conclusion, our results highlight how the proposed protocol allows for the direct connection between vibrational modes and local structural changes, providing a link from the spectroscopic observable to the structure, the peptide backbone, and its microenvironment. Full article