Search Results (2,394)

First-principles calculations based on density functional theory (DFT) are a powerful tool in data-oriented materials research. The choice of approximation for the exchange-correlation functional is crucial, as it strongly affects the accuracy of DFT calculations. This study compares the performance capabilities of three approximations on the energetics, mechanical and electronic properties, and crystal structure of NaAlP₂O₇, which is an insulator with a wide band gap that suppresses its electronic conductivity. Two of these approximations are based on Perdew–Burke–Ernzerhof (PBE) generalized gradient approximation (GGA) and the other on the strongly constrained and appropriately normed (SCAN) meta-GGA. We explore these materials as a contribution to the development of new solid electrolytes (SEs) for sodium-ion batteries (NIBs), which have the potential to mitigate challenges related to lifecycle, safety, and low ionic conductivity. The performance of these batteries largely emanates from the extraordinary demand for high-performing energy storage technologies. This study revealed that PBEsol accurately predicted lattice parameters that closely aligned with experimental values. However, r2SCAN provided the most reliable predictions of the structural and electronic properties of the NaAlP₂O₇ solid electrolyte compared to PBE and PBEsol. Findings demonstrated that the material is structurally, mechanically, electronically, and thermodynamically stable, but exhibits vibrational instability, which may scatter ions and reduce ionic conductivity due to the presence of imaginary frequencies. Our results highlight the importance of selecting appropriate functionals for solid electrolyte DFT computations. The r2SCAN functional appears to be a promising choice for calculating NaAlP₂O₇ properties. Full article

In recent years, antiaromatic compounds have gained significant attention in optoelectronic materials, catalytic synthesis, and biomedicine due to their unique electronic structures and properties, emerging as a research frontier in organic chemistry. Over the past five years, a variety of novel antiaromatic metallacycles have been reported. Their electronic structures, however, differ significantly from those of conventional antiaromatic systems due to the involvement of transition metal d orbitals. In this context, computational methods, particularly density functional theory, play an important role in evaluating and understanding antiaromaticity. This paper reviews representative examples of antiaromatic metallacycles reported in the past five years, with particular emphasis on the critical role of computational chemistry methods in characterizing their antiaromatic nature, aiming to provide valuable insights for future research in this rapidly evolving area. Full article

We studied experimentally and computationally the structures and optical properties of sulfur (S), selenium (Se) and tellurium (Te) ring clusters. We encapsulated S, Se and Te into AFI, MOR, CHA and LTA zeolites via vapor adsorption or high-pressure injection from melt and studied Raman and optical absorption spectra (RS and OAS, respectively) of zeolite single crystals with incorporated S, Se and Te ring clusters. Importantly, strict orientation of the rings in zeolite crystals allowed us to study the polarization/orientation dependency of ring RS and OAS. The obtained experimental spectra are found to be in agreement with density functional theory results (DFT using the PBE0 functional and def2-TZVP basis sets) for S₈, Se₆, Se₈, Se₁₂, Te₆ and Te₈ ring molecules. The agreement is especially good for Te rings, while for S and Se rings harmonic frequency scaling factors are required. The S and Se rings display light-induced effects, which we attribute to the presence of conical intersections between their ground and excited electronic states, resulting in isomerization and subsequent fragmentation. We consider this effect using the Se₆ ring example. This phenomenon is important for understanding photostructural changes not only in chalcogen clusters but also in bulk materials such as amorphous selenium. Full article

Scandate cathodes have garnered significant attention for their exceptional low-temperature, high-current-density emission characteristics. However, their widespread deployment in vacuum electronic devices is currently hindered by stringent vacuum requirements and susceptibility to ion bombardment. To enhance the engineering applicability of scandate cathodes, this study employs first-principles density functional theory (DFT) to model the surface microstructures of strontium (Sr)–scandium (Sc) co-doped systems. Guided by simulation predictions regarding surface elemental ratios, corresponding emission active materials and cathode samples were fabricated. A systematic comparison between theoretical calculations and experimental measurements reveals a critical trade-off: while increasing Sr content enhances structural stability (indicated by lower formation energies), it concurrently increases the work function. Consequently, an optimal Sr doping level of approximately 2 wt% is identified, which significantly improves emission current density without compromising stability. Cathodes fabricated with this optimized composition were tested in a practical electron gun configuration. Results demonstrate that under low-temperature conditions (1000 °C) and wide-pulse operation (2 ms), the cathode achieves an emission current density of 21.57 A/cm². These findings validate the efficacy of simulation-guided material design and highlight the potential of Sr-doped scandate cathodes for high-power microwave applications. Full article

Understanding the intrinsic Li–H₂ interaction, decoupled from substrate effects, is essential to rationalize the performance of lithium-decorated hydrogen storage materials. To address the current lack of a clean theoretical baseline, we characterized the sequential H₂ adsorption on the gas-phase Li₆ superatomic cluster using high-level density functional theory (DFT), complemented by Energy Decomposition Analysis (EDA), QTAIM, and NICS(0) calculations. Li₆ acts as a structurally rigid platform (RMSD < 0.032 Å) where ligand-induced polarization progressively strengthens its σ-aromaticity (NICS(0) from −2.917 to −13.98 ppm) and increases the HOMO–LUMO gap up to 5.05 eV. EDA identifies the binding as field-activated physisorption, electrostatically dominated (65–67%) and mechanistically distinct from Kubas coordination, as confirmed by QTAIM closed-shell interaction parameters. Negative cooperativity governs an effective loading capacity of n = 2 molecules under cryogenic conditions (T_eq = 143.76 and 114.64 K), while an entropic bottleneck renders higher loading non-spontaneous at all temperatures. These results establish Li₆(H₂)_n as a foundational gas-phase reference, providing a systematic, contamination-free descriptor set for the intrinsic Li–H₂ interaction. This framework is essential for isolating the electronic role of the lithium superatom and unambiguously identifying substrate-induced modulations in supported hydrogen storage materials. Full article

This paper presents a theoretical study on the electromechanical coupling response of piezoelectric–flexoelectric–semiconductor (PFS) nanocantilevers by adopting flexoelectric elasticity and semiconductor theory. A unified mechanical–electrical model is established to incorporate a strain gradient, the piezoelectric effect, semiconducting characteristics, and flexoelectricity at micro-/nanoscales. Analytical solutions for deflection, electric potential, and electron concentration are obtained under three types of electrical boundary conditions. Numerical results show that flexoelectricity significantly enhances the effective bending stiffness of the beam under open-circuit conditions with or without surface electrodes, especially in thinner structures. With a fixed external electric potential condition, the applied potential can effectively modulate the deflection by adjusting the polarization field. The induced electric potential, under the open-circuit condition with surface electrodes, exhibits a peak value at a critical thickness and flexoelectric coefficient due to the synergistic effect of the strain gradient and flexoelectricity. The electron screening effect induced by the high doping concentration is found to suppress the induced potential considerably. The present work provides a fundamental understanding of PFS coupling and provides guidance for the design of high-sensitivity micro–nano-electromechanical systems/devices. Full article

In this work, sodium alginate (NaAlg) membranes were enhanced with synthesized zinc oxide (ZnO) nanoplates to enable efficient pervaporation dehydration of isopropyl alcohol (IPA). A comprehensive suite of characterisation techniques—scanning electron (SEM) and atomic force (AFM) microscopy, Fourier-transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), contact angle and liquid uptake measurements—along with density functional theory (DFT) calculations, was employed to establish robust structure–property relationships and to elucidate filler–polymer interactions. Membranes with different ZnO contents were prepared, and membranes based on the optimal NaAlg-ZnO(5%) composite were cross-linked with CaCl₂ to improve stability in aqueous solutions, and supported membranes were developed for prospective applications by applying this composite onto the prepared porous cellulose acetate (CA) substrate. This developed cross-linked supported NaAlg-ZnO(5%)/CA membrane had a permeation flux increased by 2 times or more compared to a dense NaAlg membrane during dehydration of IPA (12–30 wt.% water) with a permeate water content above 99 wt.%. The integrated experimental–theoretical approach provides mechanistic insight into ZnO–NaAlg interactions and demonstrates the strong potential of these mixed matrix membranes for high-efficiency alcohol dehydration, offering a rational design paradigm for next-generation pervaporation membranes. Full article

Achieving high selectivity in the hydrogenation of CO₂ to light olefins remains challenging because of the complex reaction network and the difficulty of regulating key intermediates. Motivated by green-hydrogen-enabled power-to-chemicals pathways, we combine density functional theory (DFT) with first-principles microkinetic simulation (FPMS) to construct a quantitatively predictive reaction-energy landscape and elucidate structure–selectivity relationships. A comprehensive reaction network is established through energy-surface fitting, and steady-state rate constants are solved to capture the microkinetic competition between elementary steps. By introducing electronic density-of-states (DOS) modulation as a design variable, we directly correlate surface structural parameters with rate-controlling steps, thereby enabling targeted regulation of C–C coupling and hydrogen transfer processes. The calculated barrier for CO₂ adsorption to COOH* is 1.35 eV, while the transition state barrier for C–C coupling is 1.50 eV, corresponding to a reaction rate of 9.7 × 10³ s⁻¹; the olefin desorption rate reaches 1.7 × 10⁷ s⁻¹. Crucially, shifting the d-band center from −2.35 eV to −1.60 eV increases the C₂–C₄ olefin selectivity from 42.6% to 68.3%, establishing an actionable electronic structure lever for catalyst optimization. These results reveal the intrinsic mechanism by which surface electronic and geometric regulation governs intermediate stabilization and rate control, providing a verifiable, mechanism-based design principle for efficient CO₂-to-olefin catalysts aligned with green hydrogen deployment. Full article

While macroscopic stress significantly impacts the performance of metallic components, the underlying atom–electron coupling mechanisms governed by distinct crystal symmetries remain insufficiently understood. To address this gap, this work systematically investigates the structural and electronic evolution of representative metallic materials under applied stress. Experimentally, X-ray diffraction (XRD) revealed complex macroscopic residual stress distributions in cold rolled titanium alloy and silicon steel. Motivated by these engineering observations, first-principles density functional theory (DFT) calculations were conducted to uncover the underlying physical mechanisms. Specifically, the responses of face-centered cubic (FCC) aluminum and copper, body-centered cubic (BCC) iron, and hexagonal close-packed (HCP) titanium crystals were investigated under tension and compression using the RPBE functional. Stress-dependent elastic properties, density of states (DOS), band structures, and phonon spectra were calculated. Results show that tension softens all metals (Al becomes mechanically unstable), whereas compression stiffens their lattices. Electronically, tensile loading sharpens DOS peaks near the Fermi level and shifts conduction bands closer to it, whereas compression smooths DOS peaks and shifts bands away. Phonon analysis indicates Cu and Ti remain dynamically stable, while Al and Fe exhibit phonon mode softening under high tension. These stress-induced changes highlight crucial atom–electron coupling mechanisms, providing a theoretical basis for tailoring metallic performance via stress engineering. Full article

Pore structure and multifractal characteristics are two critical indicators for evaluating the heterogeneity of tight sandstone reservoirs. An integrated analysis comprising physical property tests, X-ray diffraction, casting thin sections, scanning electron microscopy, high-pressure mercury intrusion (HPMI), and constant-rate mercury intrusion (CRMI) is conducted on five samples from the Jurassic Sangonghe Formation in the northern Turpan-Hami Basin to investigate the full-scale pore size distribution (FPSD) and its multifractal characteristics. The results indicate that the pores in tight sandstone are mainly residual intergranular pores, dissolution pores, intercrystalline pores, and microfractures. The FPSD exhibits a bimodal or trimodal pattern, with dominant pore sizes ranging from 0.00516 μm to 1.15 $\mathsf{\mu }\mathrm{m}$. Two key multifractal parameters, the multifractal dimension range ($D_{min}-D_{max}$) and the relative dispersion ($R_d$), were utilized to effectively characterize pore structure heterogeneity and asymmetry. Higher $D_{min}-D_{max}$ values correspond to stronger heterogeneity, whereas lower $R_d$ values indicate a dominance of nanoscale pores. Furthermore, $D_{min}-D_{max}$ and $R_d$ exhibit negative correlations with permeability and clay mineral content, and positive correlations with feldspar content. This study demonstrates the utility of FPSD in characterizing pore structure and highlights the applicability of multifractal theory in assessing the heterogeneity of tight sandstone reservoirs. Full article

Electronic word of mouth (eWOM) and traditional word of mouth (WOM-T) are key information channels in consumer decisions, but there are still gaps in integrative models that analyze both channels simultaneously in emerging contexts. This exploratory, theory-informed study proposes a conceptual model that articulates five antecedents—satisfaction, trust, emotional bond, openness to novelty, and perceived social influence—two mediators—consumer engagement and recommendation intention—and two outcome behaviors—eWOM and traditional WOM—to examine how these variables are associated with the generation of recommendations among young/internet-connected consumers of SME services in the Lambayeque Region, Peru. Using PLS-SEM with 380 participants, 25 structural hypotheses were evaluated, including direct effects and simple and sequential mediations. In this non-probability sample, the hypothesized associations were statistically supported: antecedents were positively associated with engagement, which was positively associated with recommendation intention, which in turn predicted both online and offline WOM behaviors. Emotional bond and trust showed particularly strong effects. The model explained between 49% and 64% of the variance in endogenous variables. The findings contribute to understanding word-of-mouth dynamics in emerging markets for the studied segment of digitally connected consumers, with implications for relational marketing strategies and SDGs 8 and 12. Importantly, the contribution to SDG 12 is conditional: word-of-mouth can also amplify unsustainable consumption when recommendations are not linked to responsible practices; this caveat should be considered when interpreting the sustainability implications of these findings. Full article

First-principles calculations based on density functional theory (DFT) are performed to investigate the interfacial properties and fracture behavior of 3C-SiC(111)/Al(111) and 4H-SiC(0001)/Al(111) interfaces. To mitigate surface effects through adequate slab thickness, the interface models are constructed by positioning a seven-layer Al(111) slab atop eight-layer 3C-SiC(111) and 14-layer 4H-SiC(0001) slabs, respectively. Accounting for the distinct surface terminations and stacking sequences of each polytype, six interface configurations are established: C-top, -center, and -hollow; Si-top, -center, and -hollow. Based on the simulation results of surface energy, work of separation, and electron density distribution, the C-top configuration yields the most stable SiC/Al interface structure, exhibiting the highest work of separation. The ultimate tensile strengths of the C-top interfaces are 6.603 GPa (3C-SiC/Al) and 6.851 GPa (4H-SiC/Al), with corresponding tensile strains of 10% and 12%, respectively. Tensile fracture initiates exclusively within the Al slab for all C-top interfaces, but at distinct atomic layers: fracture occurs between the second and third Al layers (Al2–Al3) for 3C-SiC/Al; and between the first and second Al layers (Al1–Al2) for 4H-SiC/Al. This distinction reflects the influence of different interfacial configurations on the bonding strength between aluminum atomic layers. In summary, an atomic-scale investigation of the interfacial properties and fracture behavior of SiC/Al interfaces provides critical insights for the design and fabrication of novel ceramic/metal composites. Full article

The detection of sulfur hexafluoride (SF₆) decomposition products is critical for diagnosing insulation faults in gas-insulated switchgear (GIS). In this study, a vanadium-doping strategy was incorporated into the graphene/MoS₂ (GM) heterojunction to design a vanadium-doped graphene/MoS₂ (GMV) heterojunction material. Leveraging first-principles density functional theory (DFT), the adsorption behaviors of five characteristic SF₆ and its decomposition gases (H₂S, SO₂, SOF₂, SO₂F₂) on intrinsic GM and GMV were systematically investigated to evaluate their potential for gas sensing applications. Computational results reveal that intrinsic GM exhibits only weak physical adsorption toward all target molecules, with low adsorption energies and negligible charge transfer, which fails to meet practical application requirements. In contrast, GMV demonstrates significantly enhanced adsorption energies for H₂S, SO₂, and SOF₂ at vanadium sites (with a maximum value of −0.388 eV for SO₂) and shorter adsorption distances, while SO₂F₂ and SF₆ preferentially adsorb near electron-deficient carbon regions. Intrinsic GMV displays semimetallic properties, with a Fermi level at 0.126 eV and a band gap of 0.0017 eV. Upon adsorption of H₂S, SOF₂, SO₂F₂, or SF₆, the Fermi level undergoes a moderate shift (ranging from −1.083 eV to +0.349 eV), with minimal changes in the band gap. Conversely, SO₂ adsorption induces a substantial downward shift of the Fermi level to −1.732 eV, accompanied by the emergence of a sharp partial density of states (PDOS) peak near the Fermi level (0–1.5 eV), indicating strong orbital coupling and significant charge transfer. Furthermore, recovery times calculated using classical formulas show that at room temperature and a frequency of 1 × 10⁶ Hz, the recovery time of GMV for SO₂ is 2.43 s, outperforming the other four gases and satisfying practical gas sensing requirements. Through comprehensive analysis of adsorption distances, electronic structure changes, and recovery times, GMV exhibits higher selectivity toward SO₂. Thus, GMV can serve as a sensing material for detecting GIS insulation faults associated with elevated SO₂ concentrations, offering a viable strategy for advancing online monitoring technologies in power systems. Full article

A structural analysis of phenylpropanoids demonstrates that the benzene ring and the propenoic fragment act as two largely independent π-electron systems. This distinctive feature provides a theoretical basis for the rational design of novel compounds obtained through the structural integration of phenylpropanoids with polyene aldehydes and acids. These classes may be combined by elongating the carbon backbone via iterative vinyl group extension, thereby generating an expanded conjugated double-bond system. Alternatively, the structure of polyene aldehydes may be modified by replacing the unreactive methyl group with a benzene ring bearing suitable functional substituents. DFT computational studies performed at the B3LYP/QZVP level of theory indicate that the designed analogs predominantly scavenge radicals through the sequential proton loss electron transfer (SPLET) mechanism in aqueous environments. This pathway involves the initial deprotonation of carboxyl, aldehyde, or phenolic groups, with the hydroxyl moiety exhibiting the greatest propensity for proton dissociation. Carbon chain extension exerts only a minor influence on proton affinity (PA) values but significantly affects electron transfer enthalpy (ETE) parameters. Consequently, increasing the number of conjugated double bonds enhances activation of the second step of the SPLET mechanism, thereby improving overall radical-scavenging activity. Comparison of the calculated chemical reactivity parameters substantiates the conclusions drawn from the thermodynamic analysis. A pronounced enhancement in the reactivity of the modeled compounds, relative to the parent constituents, is observed. Time-dependent density functional theory (TD-DFT) calculations further predict absorption in the visible region, indicating potential applications of the modeled compounds as radical-scavenging dyes in food, pharmaceutical, cosmetic, and dietary supplement formulations. Full article

Phenetole derivatives with dual ethoxy substituents exhibit rich conformational diversity and complex vibronic characteristics, making them important model compounds for understanding substituent effects on molecular structure and spectroscopy. In this work, we systematically investigated the stable rotamers, vibronic spectra, and cationic ground-state features of p-diethoxybenzene (PDEB) using resonance-enhanced multiphoton ionization (REMPI), UV-UV hole-burning (HB), and mass-analyzed threshold ionization (MATI) spectroscopies, combined with density functional theory (DFT) calculations. The ground-state potential energy surface (PES) of PDEB was calculated at the B3LYP/6-311++G(d,p) level, identifying eight rotamers with distinct statistical weights and relative energies. Hole-burning spectroscopy resolved two dominant rotamers (cis/up–up and trans/up–down) in the supersonic molecular beam, with their S₁←S₀ transition origins determined as 33,824 cm⁻¹ and 33,613 cm⁻¹, respectively. Franck-Condon simulations of the vibronic transitions showed excellent agreement with the experimental REMPI spectra, enabling precise assignment of substituent and benzene ring vibrational modes. MATI experiments yielded accurate adiabatic ionization energies (AIEs) of the cis and trans rotamers as 59,629 ± 5 cm⁻¹ and 59,432 ± 5 cm⁻¹, respectively, and identified active cationic vibrational modes in the D₀ state. Geometric parameters of PDEB in the S₀, S₁, and D₀ states were calculated at the B3PW91/aug-cc-pVTZ, TD-B3PW91/aug-cc-pVTZ, and UB3PW91/aug-cc-pVTZ levels, revealing structural evolution during electronic excitation and ionization. The effects of ethoxy substituent orientation on molecular energy, vibrational frequencies, and ionization energy are discussed, and differences in spectral characteristics between PDEB and its meta isomer (MDEB) are compared. This work provides a comprehensive spectral and structural database for p-diethoxybenzene and deepens the understanding of structure–property relationships in diethoxybenzene isomers. Full article