Search Results (902)

Single crystals of the layered EuRECuTe₃ series with RE = Nd, Sm, Tb and Dy are obtained for the first time, completing the series of studies on quaternary tellurides synthesized using the halide flux method. These compounds crystallize in the orthorhombic space group Pnma (no. 62) with unit cell parameters ranging from a = 11.5634(7) Å, b = 4.3792(3) Å and c = 14.3781(9) Å for EuNdCuTe₃ to a = 11.2695(7) Å, b = 4.3178(3) Å and c = 14.3304(9) Å for EuDyCuTe₃. The influence of prismatic polyhedra [EuTe₆₊₁]⁷⁻ structural units on the stabilization of 3d framework composed by 2d layered fragments [RECuTe₃]²⁻, which have a key role in the interlayer interaction, is established. A comparative analysis of structural and magnetic properties dependence on the rare-earth element radius r_i(RE³⁺) in the EuRECuTe₃ series (RE = Sc, Y, Nd–Lu) is carried out. The structural contraction, including decrease in degree of tetrahedral polyhedra distortion, bond lengths shortening and unit cell volume shrinking with increasing r_i(RE³⁺), is established. It is shown that the structural alternation leads to transition from ferromagnetic to ferrimagnetic ordering. It was established that changes in the cationic sublattice have a more significant impact on structural transitions in the series of quaternary tellurides than changes in the anionic sublattice. The electronic structure and elastic and dynamic properties were estimated using ab initio calculations. The exfoliation energy for each compound is obtained by estimation of monolayer ground state energy as a result of structure relaxation. The symmetry and structural properties of monolayer EuRECuTe₃ (RE = Nd, Sm, Tb, Dy) compound are established and the orthorhombic symmetry is obtained with layer group pm2_1b. Full article

Particle Swarm Optimization (PSO) is a metaheuristic optimization technique based on population behavior, inspired by the movement of a flock of birds or a school of fish. In this method, particles move in a search space to find the global minimum of an objective function. In this work, a modified PSO algorithm written in Fortran 90 is proposed. The optimized structures obtained with this algorithm are compared with those obtained using the basin-hopping (BH) method written in Python (3.10), and complemented with density functional theory (DFT) calculations using the Gaussian 09 software. Additionally, the results are compared with the structural parameters reported from single crystal X-ray diffraction data for carbon clusters ${\mathrm{C}}_n$(n = 3–5), and tungsten–oxygen clusters, ${\mathrm{WO}}_n^{m-}$(n = 4–6, $m=2,4,6$). The PSO algorithm performs the search for the minimum energy of a harmonic potential function in a hyperdimensional space $\in {\mathbb{R}}^{3N}$ (where N is the number of atoms in the system), updating the global best position ( $g_{best}$) and local best position ( $p_{best}$), as well as the velocity and position vectors for each swarm cluster. A good approximation of the optimized structures and energies of these clusters was obtained, compared to the geometric optimization and single-point electronic energies calculated with the BH and DFT methods in the Gaussian 09 software. These results suggest that the PSO method, due to its low computational cost, could be useful for approximating a molecular structure associated with the global minimum of potential energy, accelerating the prediction of the most stable configuration or conformation, prior to ab initio electronic structure calculation. Full article

To develop single molecule magnets, a dinuclear complex [Dy₂(HOBQ)₄Cl₆] (1) was prepared from the reaction of DyCl₃ with benzo[h]quinolin-10-ol (HOBQ). Each Dy(III) ion shows a compressed octahedral geometry and the two Dy(III) ions in 1 are bridged by two Cl⁻ ligands to construct a dinuclear structure with the four HOBQ ligands on the axial positions and six Cl⁻ ligands in the equatorial plane. Magnetic measurements showed that complex 1 is a field-induced single molecule magnet having an obvious magnetic hysteresis loop with an energy barrier of 71(2) K. These experimental results are corroborated by the ab initio complete active space self-consistent field (CASSCF) calculations which also interpret the magneto-structural correlation. It is a typical example to achieve Dy(III) SMM through regulating coordination geometry, i.e., lengthening equatorial coordination bonds and shortening axial ones to form a compressed octahedral geometry. Full article

Carbon dioxide is naturally present in the Earth’s atmosphere and plays a role in regulating and balancing the planet’s temperature. However, due to various human activities, the amount of carbon dioxide is increasing beyond safe limits, disrupting the Earth’s natural temperature regulation system. Today, CO₂ is the most prevalent greenhouse gas; as its concentration rises, significant climate change occurs. Therefore, there is a need to utilize anthropogenically released carbon dioxide in valuable fuels, such as formic acid (HCOOH). Single-atom catalysts are widely used, where a single metal atom is anchored on a surface to catalyze chemical reactions. In this study, we investigated the potential of Cu@Phosphorene as a single-atom catalyst (SAC) for CO₂ reduction using quantum chemical calculations. All computations for Cu@Phosphorene were performed using density functional theory (DFT). Mechanistic studies were conducted for both bimolecular and termolecular pathways. The bimolecular mechanism involves one CO₂ and one H₂ molecule adsorbing on the surface, while the termolecular mechanism involves two CO₂ molecules adsorbing first, followed by H₂. Results indicate that the termolecular mechanism is preferred for formic acid formation due to its lower activation energy. Further analysis included charge transfer assessment via NBO, and interactions between the substrate, phosphorene, and the Cu atom were confirmed using quantum theory of atoms in molecules (QTAIM) and non-covalent interactions (NCI) analysis. Ab initio molecular dynamics (AIMD) calculations examined the temperature stability of the catalytic complex. Overall, Cu@Phosphorene appears to be an effective catalyst for converting CO₂ to formic acid and remains stable at higher temperatures, supporting efforts to mitigate climate change. Full article

The origin of chemical ordering in liquid and supercooled liquid Ge₂Sb₂Te₅ (GST) was investigated using ab initio molecular dynamics (AIMD) simulations. Bond dynamics were analyzed via continuous (${\mathrm{\tau }}_{\mathrm{con}}$) and intermittent (${\tau }_{int}$) lifetimes. The intermittent lifetime (${\tau }_{int}$) reveals that chemically ordered Ge-Te and Sb-Te bonds are the most stable, although ${\mathrm{\tau }}_{\mathrm{con}}$ exhibits a stability anomaly. The faster increase of ${\tau }_{int}$ for these bonds upon cooling explains the overall chemical ordering. A novel ordering mechanism was identified through the analysis of bond separation dynamics. Te-Te ‘wrong’ bonds exhibit a unique dynamic instability, breaking and separating much faster than any other bond type, which actively drives the system towards chemical order. A correlation between lifetime and bond strength, as calculated by the Integrated Crystal Orbital Hamilton Population (ICOHP), supports these dynamic findings. Chemical ordering shows a positive correlation with medium-range structural order, evidenced by the instability of 4-fold rings containing wrong bonds. This study provides a detailed dynamic origin for ordering in liquid GST, highlighting the role of Te-Te bond relaxation. Full article

The electrical properties of contacts to p-type nitride semiconductor devices, based on gallium nitride, were simulated by ab initio and drift-diffusion calculations. The electrical properties of the contact are shown to be dominated by the electron-transfer process from the metal to GaN, which is related to the Fermi-level difference, as determined by both ab initio and model calculations. The results indicate a high potential barrier for holes, leading to the non-Ohmic character of the contact. The electrical nature of the Ni–Au contact formed by annealing in an oxygen atmosphere was elucidated. The influence of doping on the potential profile of p-type GaN was calculated using the drift-diffusion model. The energy-barrier height and width for hole transport were determined. Based on these results, a new type of contact is proposed. The contact is created by employing multiple-layer implantation of deep acceptors. The implementation of such a design promises to attain superior characteristics (resistance) compared with other contacts used in bipolar nitride semiconductor devices. The development of such contacts will remove one of the main obstacles in the development of highly efficient nitride optoelectronic devices, both LEDs and LDs: energy loss and excessive heat production close to the multiple-quantum-well system. 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

Inner products of spherical tensor operators have been used since the early eighties to define orthogonal operators. However, the basic theory and properties are largely missing in the literature. An inner product in any configuration is directly proportional to the inner product taken in the most basic configuration in which it can occur. The formula for the proportionality factor in question is presented for the first time. This allows the inner products in and between arbitrary configurations to be calculated in advance. In addition, inner products are shown to be independent of the coupling scheme used to construct the state functions. Applications such as the orthogonal operator method and projections of ab initio calculations check for the completeness of the used basis of operators and, importantly, check the matrix elements in any arbitrary configuration, as discussed and illustrated with examples. Closed formulae for the inner products of the well-known Slater and spin–orbit operators are given. 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 dissociation of the C-NO₂ bond is the initial step in the process of the detonation of nitroaromatic explosives. The strength of the C-NO₂ bond is significantly influenced by the relative position of the nitro group with respect to the aromatic ring plane since the planar arrangement enables the delocalization of electron density, which strengthens this bond. In this study, we have combined a statistical analysis of geometrical parameters extracted from crystal structures of trinitroaromatic molecules with ab initio calculations of non-covalent index plots and Wiberg bond index values for selected trinitroaromatic molecules to elucidate the influence of nearby substituents on the relative position of nitro groups with respect to the aromatic ring plane. The results of the analysis showed that neighboring substituents have a significant impact on the geometry of nitro groups. The results also showed that this influence arises from the repulsive interaction of voluminous substituents, attractive non-covalent contacts, and the electronic effects of substituents. 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

The ${\gamma }^{\prime }$-Fe₄N system has a high technological relevance due to its multiple applications in the field of surface treatment against wear and corrosion of iron in steel parts, as well as in the manufacturing of high-density magnetic recording devices, and so on. In the present work, we present a wide research of the structural, elastic, magnetic, vibrational, and thermophysical properties by means of the phonon analysis. For these purposes, we have compared theoretical and experimental results. The theoretical data were obtained by employing ab initio electronic structure calculations in the framework of density functional theory (DFT), and different experimental measurements, such as X-ray diffraction, magnetization measurements, and calorimetric techniques, were used to characterize the ${\gamma }^{\prime }$-Fe₄N system. The resulting comparison showed an excellent agreement between the theoretical and experimental data reported. Full article

The valence-shell electronic state spectroscopy of β-butyrolactone (CH₃CHCH₂CO₂) is comprehensively investigated by employing experimental and theoretical methods. We report a novel vacuum ultraviolet (VUV) absorption spectrum in the photon wavelength range from 115 to 320 nm (3.9–10.8 eV), together with ab initio quantum chemical calculations at the time-dependent density functional (TD-DFT) level of theory. The dominant electronic excitations are assigned to mixed valence-Rydberg and Rydberg transitions. The fine structure in the CH₃CHCH₂CO₂ photoabsorption spectrum has been assigned to C=O stretching, $v_7^{\prime }\left(a\right)$, CH₂ wagging, $v_{14}^{\prime }\left(a\right)$, C–O stretching, $v_{22}^{\prime }\left(a\right)$, and C=O bending, $v_{26}^{\prime }\left(a\right)$ modes. Photolysis lifetimes in the Earth’s atmosphere from 0 km up to 50 km altitude have been estimated, showing to be a non-relevant sink mechanism compared to reactions with the ^•OH radical. The nuclear dynamics along the C=O and C–C–C coordinates have been investigated at the TD-DFT level of theory, where, upon electronic excitation, the potential energy curves show important carbonyl bond breaking and ring opening, respectively. Within such an intricate molecular landscape, the higher-lying excited electronic states may keep their original Rydberg character or may undergo Rydberg-to-valence conversion, with vibronic coupling as an important mechanism contributing to the spectrum. Full article

In this work, a comprehensive theoretical investigation is carried out to explore the electronic and spectroscopic properties of selected diatomic molecular ions MgRb⁺ and SrRb⁺. Using high-level ab initio calculations based on a pseudopotential approach, along with large Gaussian basis sets and full valence configuration interaction (FCI), we accurately determine adiabatic potential energy curves, spectroscopic constants, transition dipole moments (TDMs), and permanent electric dipole moments (PDMs). To deepen our understanding of these systems, we calculate radiative lifetimes for vibrational levels in both ground and low-lying excited electronic states. This includes evaluating spontaneous and stimulated emission rates, as well as the effects of blackbody radiation. We also compute Franck–Condon factors and analyze photoassociation processes for both ions. Furthermore, to explore low-energy collisional dynamics, we investigate elastic scattering in the first excited states (2¹Σ⁺) describing the collision between the Ra atom and Mg⁺ or Sr⁺ ions. Our findings provide detailed insights into the theoretical electronic structure of these molecular ions, paving the way for future experimental studies in the field of cold and ultracold molecular ion physics. Full article

Nanowear-resistant coatings are critical for extending the service life of mechanical components, yet their performance optimization remains challenging due to the complex interplay between atomic-scale defects and macroscopic wear behavior. While experimental characterization struggles to resolve transient interfacial phenomena, multiscale simulations, integrating ab initio calculations, molecular dynamics, and continuum mechanics, have emerged as a powerful tool to decode structure–property relationships. This review systematically compares mainstream computational methods and analyzes their coupling strategies. Through case studies on metal alloy nanocoatings, we demonstrate how machine learning-accelerated simulations enable the targeted design of layered architectures with 30% improved wear resistance. Finally, we propose a protocol combining high-throughput simulation and topology optimization to guide future coating development. Full article