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1.
Yuanchao Huang 《中国物理 B》2022,31(4):46104-046104
The p-type doping efficiency of 4H silicon carbide (4H-SiC) is rather low due to the large ionization energies of p-type dopants. Such an issue impedes the exploration of the full advantage of 4H-SiC for semiconductor devices. In this study, we show that co-doping group-IVB elements effectively decreases the ionization energy of the most widely used p-type dopant, i.e., aluminum (Al), through the defect-level repulsion between the energy levels of group-IVB elements and that of Al in 4H-SiC. Among group-IVB elements Ti has the most prominent effectiveness. Ti decreases the ionization energy of Al by nearly 50%, leading to a value as low as ~0.13 eV. As a result, the ionization rate of Al with Ti co-doping is up to ~5 times larger than that without co-doping at room temperature when the doping concentration is up to 1018 cm-3. This work may encourage the experimental co-doping of group-IVB elements such as Ti and Al to significantly improve the p-type doping efficiency of 4H-SiC.  相似文献   
2.
The first principle computational screening was performed to investigate the effect of selected dopants for Li3PS4 sulfide solid electrolyte on its ionic conductivity and stability toward moisture. The results suggest that substitution P5+ using isovalent cations whose electronegativity (EN) value is closer to the value of S has more significant effects on the ionic conductivity, whereby W5+ and Sb5+ can improve most. Similarly, aliovalent cation substitutions with compensating changes in the lithium-ion concentration, particularly those with a lower oxidation state and higher EN, such as Cu2+, effectively enhance the lithium-ion conductivity in this structure. For cation dopants, it is found that ionic conductivity improvement of Li3PS4 is the synergetic effect of EN and oxidation number of the dopant as well as the material's lattice parameter change. Oxides of the considered cation dopants can also improve the ionic conductivity of the material but have much lower lithium-ion conductivity than the cases of cation dopants. However, the metal oxide dopants, particularly those derived from soft Lewis' acid cations, show a marginal improvement in moisture stability of the Li3PS4 electrolyte. The effect of halides and metal halide dopants on the lithium-ion conductivity and moisture stability of Li3PS4 electrolyte are also studied. It is found that metal halides are more effective than any other dopants in improving the ionic conductivity of Li3PS4.  相似文献   
3.
Ab initio composite approaches have been utilized to model and predict main group thermochemistry within 1 kcal mol−1, on average, from well-established reliable experiments, primarily for molecules with less than 30 atoms. For molecules of increasing size and complexity, such as biomolecular complexes, composite methodologies have been limited in their application. Therefore, the domain-based local pair natural orbital (DLPNO) methods have been implemented within the correlation consistent composite approach (ccCA) framework, namely DLPNO-ccCA, to reduce the computational cost (disk space, CPU (central processing unit) time, memory) and predict energetic properties such as enthalpies of formation, noncovalent interactions, and conformation energies for organic biomolecular complexes including one of the largest molecules examined via composite strategies, within 1 kcal mol−1, after calibration with 119 molecules and a set of linear alkanes. © 2019 Wiley Periodicals, Inc.  相似文献   
4.
Eight-coordinated DyIII centres with D6h symmetry are expected to act as high-performance single-molecule magnets (SMMs) due to the simultaneous fulfilment of magnetic axiality and a high coordination number (a requisite for air stability). But the experimental realization is challenging due to the requirement of six coordinating atoms in the equatorial plane of the hexagonal bipyramid; this is usually too crowded for the central DyIII ion. Here a hexaaza macrocyclic Schiff base ligand and finetuned axial alkoxide/phenol-type ligands are used to show that a family of hexagonal bipyramidal DyIII complexes can be isolated. Among them, three complexes possess nearly perfect D6h local symmetry. The highest effective magnetic reversal barrier is found at 1338(3) K and an open hysteresis temperature of 6 K at the field sweeping rate of 1.2 mT s−1; this represents a new record for D6h SMMs.  相似文献   
5.
The structures and interaction energies of water clusters with ring stacking motifs are studied by using ab initio calculations. The structures of the water clusters are constructed by stacking either single rings or multi-rings of tetramer, pentamer, and hexamer. We found that, in the single-ring-stacking motif, the most stable isomers exhibit an alternative clockwise-anticlockwise stacking pattern. We also show that four-layer single-ring-stacking isomers are not energetically favorable in comparison with those of two-layer multi-ring-stacking isomers. The relative stability of the isomers is also analyzed in terms of H-bond strength and elastic distortions of the water molecules.  相似文献   
6.
Superhalogens, owing to their large electron affinity (EA, exceeding those of any halogen atom), play an essential role in physical chemistry as well as new material design. They have applications in hydrogen storage and lithium-ion batteries. Owing to the unique geometries and electronic features of magnesium-based clusters, their potential to form a new class of lithium salts has been investigated here theoretically. The idea is assessed by conducting ab initio computations on Li+/MgnF2n+1-2mOm compounds (n=2, 3; m=0-3) and analyzing their performance as potential Li-ion battery electrolytes. The Mg3F7 cluster, with large electron binding energy (EA of 7.93 eV), has been proven to serve as a building block for lithium salts. It is shown that, apart from high electronic stability, the new superhalogen-based electrolytes exhibit a set of desirable properties, including a large band gap, high electrolyte stability window, easy mobility of the Li+, and favorable insensitivity to water.  相似文献   
7.
Gaseous CePO2 has been identified by Knudsen effusion mass spectrometry during vaporization of CeO2 and magnesium diphosphate from tungsten double, two‐temperature effusion cell. Structure and molecular parameters of gaseous cerium phosphate under study were determined using quantum chemical calculations. On the basis of equilibrium constants measured for gas‐phase reaction, standard formation enthalpy of CePO2 was determined to be ?508 ± 41 kJ ? mol?1 at the temperature 298 K.  相似文献   
8.
There is an ongoing effort to replace rare and expensive noble-element catalysts with more abundant and less expensive transition metal oxides. With this goal in mind, the intrinsic defects of a rhombohedral perovskite-like structure of LaMnO3 and their implications on CO catalytic properties were studied. Surface thermodynamic stability as a function of pressure (P) and temperature (T) were calculated to find the most stable surface under reaction conditions (P=0.2 atm, T=323 K to 673 K). Crystallographic planes (100), (111), (110), and (211) were evaluated and it was found that (110) with MnO2 termination was the most stable under reaction conditions. Adsorption energies of O2 and CO on (110) as well as the effect of intrinsic defects such as Mn and O vacancies were also calculated. It was found that O vacancies favor the interaction of CO on the surface, whereas Mn vacancies can favor the formation of carbonate species.  相似文献   
9.
Raman and Raman Optical Activity (ROA) spectra of N-acetyl-L-cysteine (NALC), a flexible chiral molecule, were measured in water and in methanol to evaluate the solvent effects. Two different solvation approaches, that is, the DFT based “clusters-in-a-liquid” solvent model and the ab initio molecular dynamics (AIMD) simulations, were applied to simulate the Raman and ROA spectra. Systematic conformational searches were carried out using a recently developed conformational searching tool, CREST, with the inclusion of polarizable continuum model of water and of methanol. The CREST candidates of NALC and the NALC-solvent complexes were re-optimized and their Raman and ROA simulations were done at the B3LYP−D3BJ/def2-TZVP and the B3LYP-aug-cc-pVDZ//cc-pVTZ levels. Also, AIMD simulations, which includes some anharmonic effects and all intermolecular interactions in solution, were performed. By empirically weighting the computed Raman and ROA spectra of each conformer, good agreements with the experimental data were achieved with both approaches, while AIMD offered some improvements in the carbonyl and in the low wavenumber regions over the static DFT approach. The pros and cons of these two different approaches for accounting the solvent effects on Raman and ROA of this flexible chiral system will also be discussed.  相似文献   
10.
The theoretical predictions and experimental synthesis of H3S and LaH10 superconductors with record high superconducting transition temperatures (Tc) have promoted the hydrogen-based superconducors to be a research hotspot in the field of solid-state physics. Here, we predict an unprecedented layered structure CaH15, with high Tc of 189 K at 200 GPa using ab initio calculations. As concerns the novel structure, one layer is made of a hydrogen nonagon, the other layer consists of a Ca atom and six H2 molecular units surrounding the Ca atom. This layered structure was also found in SrH15, YH15, and LaH15 at high pressures, each materials exhibit high Tc especially YH15 can reach above 200 K at 220 GPa. It represents the second class of layered superhydrides with high value of Tc after pentagraphene like HfH10.  相似文献   
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