Search Results (136)

Based on density functional theory, the structural, mechanical, and photoelectric properties of the perovskite material Cs₂SeCl₆ were systematically studied under pressures ranging from 0 to 50 GPa. Analysis of structural parameters indicates that the lattice constant, unit cell volume, and bond length decrease progressively with increasing pressure. Notably, the material maintains structural stability across the entire pressure range. Electronic property calculations show that Cs₂SeCl₆ retains an indirect band gap under pressure, with the band gap value monotonically decreasing as pressure increases. The orbital contributions remain almost unchanged at different pressures. The conduction band is mainly composed of Cl-p and Se-p orbitals, while the valence band is dominated by Cl-p orbitals. The analysis of the effective mass indicates that the transport capability of charge carriers is enhanced under compression. Mechanical stability and ductility were evaluated by calculating the elastic constants and derived mechanical moduli, confirming that the material remains mechanically stable under high pressure. Optical properties were investigated by computing the dielectric function, reflectivity, refractive index, optical absorption coefficient, and extinction coefficient. Collectively, the findings of this work demonstrate that the pressurized Cs₂SeCl₆ exhibits excellent structural robustness, improved charge transport, and promising photoelectric performance, making it a strong candidate for applications in solar cells and other photoelectronic devices. Full article

In this study, density functional theory (DFT) within the generalized gradient approximation (GGA) is employed to investigate the structural, electronic, mechanical, and thermoelectric properties of perovskite hydrides XZrH₃ (X = Mg, Ca, Sr, Ba). Mechanical stability and ductility are evaluated through the Cauchy pressure, Pugh’s ratio, and Poisson’s ratio, all of which point to ductile behavior with a dominant ionic-bonding character. Electronic structure calculations reveal metallic behavior arising from band overlap at the Fermi level. Equilibrium energy–volume data are fitted with the Murnaghan equation of state, and transport coefficients are extracted using the BoltzTraP package as implemented in WIEN2k. The absence of a band gap and the overlap between valence and conduction bands confirm conductor-like behavior. Lattice thermal conductivity for MgZrH₃, CaZrH₃, SrZrH₃, and BaZrH₃ increases monotonically with temperature. Overall, the results identify MgZrH₃ in particular as a promising candidate for thermoelectric devices and solid-state hydrogen storage, thereby supporting progress toward a sustainable hydrogen economy. Full article

The pursuit of high-energy-density cathode materials has positioned LiNiO₂ as a promising candidate due to its high theoretical capacity. However, its practical application is hindered by structural instability, cation mixing, and sluggish Li-ion mobility. This study presents a strategic co-doping approach to enhance the electrochemical performance of R3m-structured LiNiO₂ by introducing Na at the Li site and Nb/Al/W at the Ni site. First-principles calculations based on density functional theory (DFT), combined with the bond valence sum energy (BVSE) method, were employed to evaluate the structural, electronic, and transport properties of the doped systems. The optimized lattice parameters reveal that co-doping induces lattice expansion and suppresses cation disorder, thereby improving structural integrity. Formation energy validates the thermodynamics of the modified structures. Furthermore, BVSE-based ion migration mapping shows that Na/Nb and Na/Al co-doping significantly broadens Li-ion diffusion pathways and lowers migration barriers compared to pristine LiNiO₂. These results demonstrate that dual-site doping is an effective strategy to overcome intrinsic limitations of Ni-rich layered oxides, offering a rational design route cathode for next-generation Li-ion battery. Full article

The development of lithium-ion batteries necessitates cathode materials that possess excellent mechanical and thermal properties in addition to electrochemical performance. As a prominent functional ceramic, the properties of spinel LiMn₂O₄ are governed by its atomic-level structure. This study systematically investigates the impact of Ni doping concentration on the mechanical and thermal properties of spinel LiNi_xMn_2−xO₄ via first-principles calculations combined with the bond valence model. The results suggest that when x = 0.25, the LiNi_xMn_2−xO₄ shows excellent mechanical properties, including a high bulk modulus and hardness, due to the favorable ratio of bond valence to bonds length in octahedra. Furthermore, this optimized composition shows a lower thermal expansion coefficient. Additionally, Ni doping concentration has a very minimal influence on the maximum tolerable temperature of the cathode material during rapid heating. Therefore, from the perspective of mechanical and thermal properties, this composition could be beneficial for improving the cycling life of the battery, since comparatively inferior mechanical properties and a higher thermal expansion coefficient make it prone to microcrack formation during charge–discharge cycles. Full article

Tennantite (Cu₁₂As₄S₁₃) and enargite (Cu₃AsS₄) are two important minerals that simultaneously contain copper and arsenic. Detailed studies of their structure and properties are crucial for understanding their oxidation, flotation, and leaching. This study investigates the crystal structures, electronic properties, and reactivity of these two copper-arsenic minerals from the perspectives of atomic bonding, charge, density of states, and d-orbital splitting. The results indicate that tennantite is a crystal with mixed Cu valence states of +2 and +1 (predominantly +1), while the Cu in enargite is in the +1 state. The valence state of As in tennantite (+3) is lower than that in enargite (+5). Orbital energy level calculations show that the energy gaps between the copper d-orbitals are small in both minerals, indicating strong electron delocalization and, consequently, strong covalent character in the crystals, which is also confirmed by Mulliken bond population calculations. The presence of arsenic is the reason for the enhanced covalency. It is noteworthy that tennantite exhibits stronger covalency. The Cu 3d and As 4p electrons in tennantite are more electronically active than those in enargite. In tennantite, the strong d-electron delocalization caused by d-p hybridization between Cu and S leads to similar 3d electronic properties between 3-coordinated and 4-coordinated Cu. The energies of the five d-orbitals of the 4-coordinated Cu in enargite are lower than those of the 4-coordinated Cu in tennantite, which may affect the ability of Cu 3d electrons to enter the empty orbitals of S atoms in sulfur-containing collectors to form π back-bonding, thereby reducing the collecting ability of enargite. On the other hand, the splitting energy of the 4-coordinated Cu 3d orbitals in enargite is significantly smaller than that in tennantite, making the structure less stable and, thus, potentially more prone to dissolution. Full article

Photoactivatable nitric oxide donors (photoNORMs) are promising agents for controlled NO release and real-time optical tracking in biomedical theranostics. Here, we report a comprehensive density functional theory (DFT) and time-dependent DFT (TDDFT) study on a series of hybrid ruthenium–gold nanocluster systems of the general formula [(L)Ru(NO)(SH)@Au₂₀], where L = salen, bpb, porphyrin, or phthalocyanine. Structural and bonding analyses reveal that the Ru–NO bond maintains a formal {RuNO}⁶ configuration with pronounced Ru → π*(NO) backbonding, leading to partial reduction of the NO ligand and an elongated N–O bond. Natural Bond Orbital (NBO), Natural Energy Decomposition Analysis (NEDA), and Extended Transition State–Natural Orbitals for Chemical Valence (ETS–NOCV) analyses confirm that Ru–NO bonding is dominated by charge-transfer and polarization components, while Ru–S and Au–S linkages exhibit a delocalized, donor–acceptor character coupling the molecular chromophore with the metallic cluster. TDDFT results reproduce visible–near-infrared (NIR) absorption features arising from mixed metal-to-ligand and cluster-mediated charge-transfer transitions. The calculated zero–zero transition and reorganization energies predict NIR-II emission (1.8–3.8 μm), a region of high biomedical transparency, making these systems ideal candidates for luminescence-based NO sensing and therapy. This study establishes fundamental design principles for next-generation Ru-based photoNORMs integrated with plasmonic gold nanoclusters, highlighting their potential as multifunctional, optically trackable theranostic platforms. Full article

The activation of carbon dioxide by transition metal complexes is a fundamental process in catalysis and carbon capture. In this study, density functional theory (DFT) calculations, combined with Quantum Theory of Atoms in Molecules (QTAIM) and Natural Orbitals for Chemical Valency (NOCV) analyses, were employed to investigate the bonding characteristics and electronic structure of Fe(0)–, Pd(0)–, and Pt(0)–phosphine complexes with CO₂. The Fe(0) complexes exhibited the strongest CO₂ activation, characterized by substantial C=O bond elongation, significant charge transfer, and strong $\pi$-backdonation. In contrast, Pd(0) complexes showed minimal CO₂ activation, while Pt(0) complexes displayed intermediate behavior. The electronic effects of phosphine ligands were also analyzed, revealing that electron-donating phosphines enhance CO₂ activation, whereas electron-withdrawing phosphines weaken metal–CO₂ interactions. These findings provide key insights into the design of transition-metal-based catalysts for CO₂ conversion and utilization. Full article

In the present work we investigate by first principles calculations the structural, electronic, and optical properties of alkyl, 1-alkenyl and 1-alkynyl C₈ moieties chemisorbed on hydrogen-terminated silicon nanowire oriented along the ⟨112⟩ direction. Our results disclose how the nature of the carbon–carbon bond contiguous to the Si surface influences the behavior of the system. While 1-alkynyl groups exhibit the strongest Si–C bonding, it is 1-alkenyl functionalization that induces the most significant enhancement in optical absorption within the visible range due to charge transfer. The charge transferred from the nanowire to the moiety confirms the electronic coupling of the two systems. We found that the highest occupied molecular orbital of the 1-alkenyl moiety lies only 0.3 eV below the valence band edge of the hydrogen-terminated silicon nanowire, enabling new low-energy optical transitions which are absent in both the unmodified silicon nanowire and the isolated molecule. These findings demonstrate a synergistic effect of functionalization. Our study provides valuable insights into the design of functionalized silicon nanostructures with tailored optical properties, with potential implications for applications in sensing, photonics, and energy conversion. Full article

Molecular geometry, infrared (IR) vibrational frequencies, and ultraviolet–visible (UV-Vis) electronic absorption spectra of the trivalent iron tris(acetylacetonate) complex, Fe(III)(acac)₃, were computed using hybrid meta-generalized gradient approximation (meta-GGA) density functional theory (DFT). Calculations employed the Jorge double-$\zeta$ valence plus polarization basis sets (standard DZP and relativistic DZP + DKH). Solvent effects were modeled using the SMD continuum solvation framework with acetonitrile as the dielectric medium. This charge-neutral complex exhibits predominantly ionic metal–ligand bonding character, which simplifies the computational treatment. Despite extensive DFT applications to coordination compounds, systematic benchmarks for this bidentate ligand system remain limited. The computed harmonic frequencies ($\nu$) and electronic excitation energies (${\lambda }_{\max }$) demonstrate excellent agreement with available experimental measurements. These results enable comparative analysis of IR and UV-Vis spectral features, both with and without all-electron scalar relativistic effects with the second-order Douglas–Kroll–Hess approach. Full article

Lanthanum-cerium rare earth (RE) elements play a vital role in metallurgy as essential microalloying elements. Their addition significantly modifies inclusion characteristics, enhances mechanical properties, and improves corrosion resistance. This review emphasizes the distinct and synergistic roles of lanthanum (La) and cerium (Ce) in steel at the atomic scale, elucidated through first-principles calculations based on density-functional theory (DFT). The primary focus includes the nucleation mechanisms and characteristics of rare earth inclusions, the solid solution and segregation behavior of rare earth atoms, and their microalloying effects on electronic structure and interfacial bonding. Although both elements form stable inclusions Re₂O₃ and ReAlO₃ and exhibit grain refinement effects, Ce exhibits a unique dual valence state (Ce³⁺/Ce⁴⁺). This results in nucleation behavior and oxide stability for Ce ions that differ slightly from those of La. Both elements alter the electronic structure of the Fe matrix through hybridization with d-orbitals, reducing magnetic moment and enhancing toughness. Compared to other alloying elements, La and Ce exhibit unique behaviors due to their large atomic radii and high chemical reactivity, which influence their solid solubility, segregation tendencies, and interactions with other atoms such as Cr, C, and N. Finally, this paper discusses the challenges that exist when first-principles computational methods are used to study the mechanism of action of RE elements in steel, and proposes measures and methods to address these challenges, aiming to provide an in-depth understanding of the mechanism of action of REs in steel at the microscopic level and to promote the application of computational chemistry in the field of metallurgy. Full article

Using density functional theory (M06-2X-D3/def2-TZVP), we investigated the 1,2-addition reactions of NH₃ with a series of heavy imine analogues, G13=P-Rea (where G13 denotes a Group 13 element; Rea = reactant), featuring a mixed G13–P–Ga backbone. Theoretical analyses revealed that the bonding nature of the G13=P moiety in G13=P-Rea molecules varies with the identity of the Group 13 center. For G13=B, Al, Ga, and In, the bonding is best described as a donor–acceptor (singlet–singlet) interaction, whereas for G13=Tl, it is characterized by an electron-sharing (triplet–triplet) interaction. According to our theoretical studies, all G13=P-Rea species—except the Tl=P analogue—undergo 1,2-addition with NH₃ under favorable energetic conditions. Energy decomposition analysis combined with natural orbitals for chemical valence (EDA–NOCV), along with frontier molecular orbital (FMO) theory, reveals that the primary bonding interaction in these reactions originates from electron donation by the lone pair on the nitrogen atom of NH₃ into the vacant p-π* orbital on the G13 center. In contrast, a secondary, weaker interaction involves electron donation from the phosphorus lone pair of the G13=P-Rea species into the empty σ* orbital of the N–H bond in NH₃. The calculated activation barriers are primarily governed by the deformation energy of ammonia. Specifically, as the atomic weight of the G13 element increases, the atomic radius and G13–P bond length also increase, requiring a greater distortion of the H₂N–H bond to reach the transition state. This leads to a higher geometrical deformation energy of NH₃, thereby increasing the activation barrier for the 1,2-addition reaction involving these Lewis base-stabilized, heavy imine-like G13=P-Rea molecules and ammonia. 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

Microwave dielectric ceramics are indispensable in modern communication technologies, playing a pivotal role in components such as filters, oscillators, and antennas. Among these materials, ZnAl₂O₄ ceramics have garnered attention for their excellent quality factor (Q × f) and low dielectric constant (ε_r). However, their high sintering temperature (~1650 °C) limits practical applications. This study investigates ZnAl_2-x(Zn_0.5Si_0.5)_xO₄ (ZAZS) (x = 0.1–0.9) ceramics, where [Zn_0.5Si_0.5]³⁺ substitutes Al³⁺, to reduce sintering temperature while maintaining high-performance microwave dielectric properties. ZAZS ceramics were synthesized via the solid-state reaction method and characterized for their structural, morphological, and dielectric properties. X-ray diffraction analysis confirmed the formation of a single-phase solid solution up to x = 0.8, with minor secondary phases appearing at x = 0.9. The substitution increased lattice parameters and enhanced material densification, as observed through SEM and relative density calculations. Microwave dielectric measurements showed that ZAZS ceramics achieved a maximum Q × f of 20,200 GHz and a τ_f value reduced to −62 ppm/°C at x = 0.8, while ε_r decreased from 7.90 to 6.98. Bond-valence calculations reveal that the reduction of the average Al/Zn/Si–O bond valence weakens octahedral rigidity, systematically tuning τ_f toward zero. These results demonstrate that ZAZS ceramics, with a reduced sintering temperature of 1400 °C, exhibit excellent potential for application in low-loss microwave devices. Full article

Recent measurements of the band properties of AlN and GaN by fluorescence yield absorption and soft X-ray emission spectroscopies revealed that their valence band (VB) is composed of two separate subbands. The upper VB subband of GaN is composed of gallium sp and nitrogen p orbitals; the lower subband consists of metal d and nitrogen s orbitals. These findings were confirmed by extensive ab initio simulations. These results are not consistent with the standard tetrahedrally coordinated semiconductors, which are bonded by sp³-hybridized orbitals of metal and nonmetal atoms. The new analysis techniques and ab initio simulations create a new picture, allowing the calculation of overlap integrals to determine the bond order in these crystals. According to these results, bonding occurs between resonant p-states of nitrogen and sp³-hybridized metal orbitals in tetrahedral nitrides, allowing tetrahedral symmetry to be maintained. A similar resonant bonding mechanism is observed in hexagonal BN, where the p orbitals of nitrogen create three resonant states necessary for maintaining the planar symmetry of the lattice. In addition, nonresonant $\pi$-type bonds in BN are created by the overlap of $p_z$ orbitals of boron and nitrogen. BN bonding differs from that in graphene, where carbon states are fully sp²-hybridized. Additionally, $\pi$-type bonds in graphene have no ionic contributions, which leads to the formation of Dirac states with linear dispersion close to the K point, closing the band gap. Full article

A comprehensive investigation of the chemical bonding, electronic structure, and spectroscopic properties of the lanarkite-type Pb₂SO₅ (PSO) structure was conducted, for the first time, using density functional theory simulations. Thus, different functionals, PBE, PBE0, PBESOL, PBESOL0, BLYP, WC1LYP, and B3LYP, were used, and their results were compared to predict their fundamental properties accurately. All DFT calculations were performed using a triple-zeta valence plus polarization basis set. Among all the DFT functionals, PBE0 showed the best agreement with the experimental and theoretical data available in the literature. Our results also reveal that the [PbO₅] clusters were formed with five Pb–O bond lengths, with values of 2.29, 2.35, 2.57, 2.60, and 2.79 Å. Meanwhile, the [SO₄] clusters exhibited uniform S–O bond lengths of 1.54 Å. Also, a complete topological analysis based on Bader’s Quantum Theory of Atoms in Molecules (QTAIM) was applied to identify atom–atom interactions in the covalent and non-covalent interactions of the PSO structure. Additionally, PSO has an indirect band gap energy of 4.83 eV and an effective mass ratio ($m_h^{*}$/$m_e^{*}$) of about 0.192 (PBE0) which may, in principle, indicate a low degree of recombination of electron–hole pairs in the lanarkite structure. This study represents the first comprehensive DFT investigation of Pb₂SO₅ reported in the literature, providing fundamental insights into its electronic and structural properties. Full article