In this work, we have employed the first‐principles calculations to investigate the phase stability and mechanical and optoelectronic characteristics of Hf2AX (A═Al, Si and X═C, N) MAX phases. Phase ...stabilities of Hf2AX compounds have been evaluated by the formation enthalpy computations and phonon dispersion curves, which indicate that all studied compounds are structurally and dynamically stable. The mechanical stability has been determined by elastic stiffness constants, which confirms that the studied MAX phases are mechanically stable. The computed results for Pugh's and Poisson ratios indicate the brittle nature of Hf2AX MAX phases. It is interesting to note that Si‐based MAX phases possess high values of B/G, indicating that they are harder than Al‐based compounds. The obtained band structures and partial density of states indicate the metallic character of all Hf2AX compounds. The strong hybridization of d‐orbitals of Hf with p‐orbitals of N and the comparatively weaker hybridization of p‐orbitals (Hf) with Al/Si p‐orbitals is observed. The presence of pseudogaps near the Fermi energy level emerges due to the orbital hybridization involving Hf, Al/Si, and C/N atoms. The analysis of charge density difference maps reveals the presence of a strong covalent bond between the Hf and C/N atoms, whereas a relatively weaker covalent bond is seen between the Hf and Al/Si atoms. Furthermore, numerous optical characteristics have been investigated to account for the behavior of the Hf2AX compounds to those of impinging electromagnetic rays. The highest absorptivity is noticed within the energy range of 7.5–12.5 eV. The optical spectra in the range of 1.7 eV (IR) to 9 eV ultraviolet (UV) have been observed for the investigated MAX phases, predicting their suitability as proficient energy absorbers within the UV region. The Intriguing properties of Hf2AX compounds are anticipated to be appropriate materials for a variety of applications.
The formation possibility of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high‐entropy ceramic (HHC‐1) was first analyzed by the first‐principles calculations, and then, it was successfully fabricated by ...hot‐pressing sintering technique at 2073 K under a pressure of 30 MPa. The first‐principles calculation results showed that the mixing enthalpy and mixing entropy of HHC‐1 were −0.869 ± 0.290 kJ/mol and 0.805R, respectively. The experimental results showed that the as‐prepared HHC‐1 not only had an interesting single rock‐salt crystal structure of metal carbides but also possessed high compositional uniformity from nanoscale to microscale. By taking advantage of these unique features, it exhibited extremely high nanohardness of 40.6 ± 0.6 GPa and elastic modulus in the range from 514 ± 10 to 522 ± 10 GPa and relatively high electrical resistivity of 91 ± 1.3 μΩ·cm, which could be due to the presence of solid solution effects.
An intricate sea-urchin-like hexagonal WO3 nanostructure was synthesized by a facile hydrothermal approach. Sensing properties of the as-fabricated sensor exhibited surpassing response and ...selectivity for NO2 in comparison of H2 after corroborating the composition, phase-purity and surface morphology using X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Formation of the urchin-like structure was ascribed to the capping effects of potassium sulfate that prompts the anisotropic growth of WO3, leading to hierarchical complex with a large surface-volume ratio. In particular, first-principle calculation had provided a new perspective for us to delve into the sensing process of H2 and NO2 from an atomic level. It was found that the sensing properties mainly arose from the tuning of electronic structure and electrons transfer between the adsorbed gas and the sensitized surface along with the charge relocation between them. Finally, a plausible mechanism was proposed as theoretical guidance for achieving high-performance sensors experimentally and supposedly.
We study the band topology and the associated linking structure of topological semimetals with nodal lines carrying Z2 monopole charges, which can be realized in three-dimensional systems invariant ...under the combination of inversion P and time reversal T when spin-orbit coupling is negligible. In contrast to the well-known PT-symmetric nodal lines protected only by the π Berry phase, in which a single nodal line can exist, the nodal lines with Z2 monopole charges should always exist in pairs. We show that a pair of nodal lines with Z2 monopole charges is created by a double band inversion process and that the resulting nodal lines are always linked by another nodal line formed between the two topmost occupied bands. It is shown that both the linking structure and the Z2 monopole charge are the manifestation of the nontrivial band topology characterized by the second Stiefel-Whitney class, which can be read off from the Wilson loop spectrum. We show that the second Stiefel-Whitney class can serve as a well-defined topological invariant of a PT-invariant two-dimensional insulator in the absence of Berry phase. Based on this, we propose that pair creation and annihilation of nodal lines with Z2 monopole charges can mediate a topological phase transition between a normal insulator and a three-dimensional weak Stiefel-Whitney insulator. Moreover, using first-principles calculations, we predict ABC-stacked graphdiyne as a nodal line semimetal (NLSM) with Z2 monopole charges having the linking structure. Finally, we develop a formula for computing the second Stiefel-Whitney class based on parity eigenvalues at inversion-invariant momenta, which is used to prove the quantized bulk magnetoelectric response of NLSMs with Z2 monopole charges under a T-breaking perturbation.
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Density functional theory calculations are robust tools to explore the mechanical properties of pristine structures at their ground state but become exceedingly expensive for large systems at finite ...temperatures. Classical molecular dynamics (CMD) simulations offer the possibility to study larger systems at elevated temperatures, but they require accurate interatomic potentials. Herein the authors propose the concept of first‐principles multiscale modeling of mechanical properties, where ab initio level of accuracy is hierarchically bridged to explore the mechanical/failure response of macroscopic systems. It is demonstrated that machine‐learning interatomic potentials (MLIPs) fitted to ab initio datasets play a pivotal role in achieving this goal. To practically illustrate this novel possibility, the mechanical/failure response of graphene/borophene coplanar heterostructures is examined. It is shown that MLIPs conveniently outperform popular CMD models for graphene and borophene and they can evaluate the mechanical properties of pristine and heterostructure phases at room temperature. Based on the information provided by the MLIP‐based CMD, continuum models of heterostructures using the finite element method can be constructed. The study highlights that MLIPs were the missing block for conducting first‐principles multiscale modeling, and their employment empowers a straightforward route to bridge ab initio level accuracy and flexibility to explore the mechanical/failure response of nanostructures at continuum scale.
A robust concept of first‐principles multiscale modeling of mechanical properties based on machine‐learning interatomic potentials conveniently trainable over short ab initio datasets is proposed. It is shown that mechanical/failure responses of complex nanostructures at continuum scale and high temperatures can be explored with the precision of sophisticated first‐principles calculations, affordable computational cost, and without the need for empirical data.
Correction for ‘p-Type conductivity mechanism and defect structure of nitrogen-doped LiNbO3 from first-principles calculations’ by Weiwei Wang et al., Phys. Chem. Chem. Phys., 2020, 22, 20–27.
While ceramic materials are widely used in our society, their understanding of the plasticity is not fully understood. MgO is one of the prototypical ceramics, extensively investigated experimentally ...and theoretically. However, there is still controversy over whether edge or screw dislocations glide more easily. In this study, we directly model the atomic structures of the dislocation cores in MgO based on the first-principles calculations and estimate the Peierls stresses. Our results reveal that the screw dislocation on the primary slip system exhibits a smaller Peierls stress than the edge dislocation. The tendency is not consistent with metals, but rather with TiN, suggesting a characteristic inherent to rock-salt type materials.
Nonlinear optical (NLO) materials are of great importance for applications in lasers, atomic clocks, free‐space communication, etc. Herein, inspired by the recent prediction of excellent second ...harmonic generation (SHG) performance in van der Waals (vdW) materials with 1D building blocks, 14 new NLO materials are found from 244 bulk crystals constructed with 1D polymers using high‐throughput first‐principles calculations. Nearly half of the new NLO materials exhibit superior NLO performance with SHG susceptibilities approaching the theoretical upper limit. The 2D form of 11 candidates inherits the NLO property covering UV, visible, and infrared regions. Bader charge analysis reveals that the SHG susceptibility is determined by the charge difference of ions on the chains. Finally, it is proposed that superior NLO materials can be found in materials with proper bandgaps and large charge differences on the chains. This work not only screens out candidates with outstanding NLO performance in vdW materials with 1D building blocks but also provides a guideline for the search and design of NLO vdW 1D polymer patterns with excellent NLO properties.
By screening bulk van der Waals (vdW) materials featuring 1D chains, materials with exceptional properties are identified, including large second harmonic generation (SHG) susceptibility, appropriate bandgap, and birefringence. These materials' nonlinear optical (NLO) properties are intricately linked to the stacking prototypes of their chains and the charge difference of ions on the chains.
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