Generalized gradient approximation adjusted to transition metals properties: Key roles of exchange and local spin density

Perdew-Burke-Ernzerhof (PBE) and PBE adapted for solids (PBEsol) are exchange-correlation (xc) functionals widely used in density functional theory simulations. Their differences are the exchange, μ, and correlation, β, coefficients, causing PBEsol to lose the Local Spin Density (LSD) response. Here, the μ/β two-dimensional (2D) accuracy landscape is analyzed between PBE and PBEsol xc functional limits for 27 transition metal (TM) bulks, as well as for 81 TM surfaces. Several properties are analyzed, including the shortest interatomic distances, cohesive energies, and bulk moduli for TM bulks, and surface relaxation degree, surface energies, and work functions for TM surfaces. The exploration, comparing the accuracy degree with respect experimental values, reveals that the found xc minimum, called VV, being a PBE variant, represents an improvement of 5% in mean absolute percentage error terms, whereas this improvement reaches ~11% for VVsol, a xc resulting from the restoration of LSD response in PBEsol, and so regarded as its variant.     

基于NiCo2O4纳米片电极的非对称混合电容器

The looming global energy crisis and ever-increasing energy demands have catalyzed the development of renewable energy storage systems. In this regard, supercapacitors (SCs) have attracted widespread attention because of their advantageous attributes such as high power density, excellent cycle stability, and environmental friendliness. However, SCs exhibit low energy density and it is important to optimize electrode materials to improve the overall performance of these devices. Among the various electrode materials available, spinel nickel cobaltate (NiCo₂O₄) is particularly interesting because of its excellent theoretical capacitance. Based on the understanding that the performances of the electrode materials strongly depend on their morphologies and structures, in this study, we successfully synthesized NiCo₂O₄ nanosheets on Ni foam via a simple hydrothermal route followed by calcination. The structures and morphologies of the as-synthesized products were characterized by X-ray diffraction, scanning electron microscopy, and Brunauer-Emmett-Teller (BET) surface area analysis, and the results showed that they were uniformly distributed on the Ni foam support. The surface chemical states of the elements in the samples were identified by X-ray photoelectron spectroscopy. The as-synthesized NiCo₂O₄ products were then tested as cathode materials for supercapacitors in a traditional three-electrode system. The electrochemical performances of the NiCo₂O₄ electrode materials were studied and the area capacitance was found to be 1.26 C·cm^-2 at a current density of 1 mA·cm^-2. Furthermore, outstanding cycling stability with 97.6% retention of the initial discharge capacitance after 10000 cycles and excellent rate performance (67.5% capacitance retention with the current density from 1 to 14 mA·cm^-2) were achieved. It was found that the Ni foam supporting the NiCo₂O₄ nanosheets increased the conductivity of the electrode materials. However, it is worth noting that the contribution of nickel foam to the areal capacitance of the electrode materials was almost zero during the charge and discharge processes. To further investigate the practical application of the as-synthesized NiCo₂O₄ nanosheets-based electrode, a device was assembled with the as-prepared samples as the positive electrode and active carbon (AC) as the negative electrode. The assembled supercapacitor showed energy densities of 0.14 and 0.09 Wh·cm^-3 at 1.56 and 4.5 W·cm^-3, respectively. Furthermore, it was able to maintain 95% of its initial specific capacitance after 10000 cycles. The excellent electrochemical performance of the NiCo₂O₄ nanosheets could be ascribed to their unique spatial structure composed of interconnected ultrathin nanosheets, which facilitated electron transportation and ion penetration, suggesting their potential applications as electrode materials for high performance supercapacitors. The present synthetic route can be extended to other ternary transition metal oxides/sulfides for future energy storage devices and systems.     

Dinuclear gold (I)-di-N-heterocyclic carbene complexes: syntheses,structure, density functional theory calculation and photoluminescence study

The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, ¹H- and ¹³C-NMR data. The ¹³C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]₂·2PF₆ is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λ_em = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm.     

NIFTy 3 – Numerical Information Field Theory: A Python Framework for Multicomponent Signal Inference on HPC Clusters

NIFTy , “Numerical Information Field Theory,” is a software framework designed to ease the development and implementation of field inference algorithms. Field equations are formulated independently of the underlying spatial geometry allowing the user to focus on the algorithmic design. Under the hood, NIFTy ensures that the discretization of the implemented equations is consistent. This enables the user to prototype an algorithm rapidly in 1D and then apply it to high‐dimensional real‐world problems. This paper introduces NIFTy  3, a major upgrade to the original NIFTy  framework. NIFTy  3 allows the user to run inference algorithms on massively parallel high performance computing clusters without changing the implementation of the field equations. It supports n‐dimensional Cartesian spaces, spherical spaces, power spaces, and product spaces as well as transforms to their harmonic counterparts. Furthermore, NIFTy  3 is able to handle non‐scalar fields, such as vector or tensor fields. The functionality and performance of the software package is demonstrated with example code, which implements a mock inference inspired by a real‐world algorithm from the realm of information field theory. NIFTy  3 is open‐source software available under the GNU General Public License v3 (GPL‐3) at https://gitlab.mpcdf.mpg.de/ift/NIFTy/tree/NIFTy_3 .     

Development and validation of an ultra‐high‐performance liquid chromatography–tandem mass spectrometry method to determine the bioavailability of warfarin and its major metabolite 7‐hydroxy warfarin in rats dosed with oral formulations containing different polymorphic forms

A simple, sensitive and rapid ultra‐high‐performance liquid chromatography–electrospray ionization–tandem mass spectrometry method was developed and validated for the quantification of warfarin and 7‐hydroxy warfarin in Sprague Dawley (SD) rats. Animals were administered a single dose of warfarin sodium formulations (crystalline and amorphous) at 12 mg/kg via oral gavage and blood was drawn over a 96‐h time course. Sample process recoveries, matrix effect and analyte stability were determined. The linearity for warfarin and 7‐hydroxy warfarin was from 5 to 2000 ng/mL in blank SD rat plasma. Correlation coefficients (r²) for standard calibration curves were >.98 and analytes quantified within ±15% of target at all calibrator concentrations. The average percent accuracy and precision for intra‐ and inter‐day were 93.7%–113.8% and ≤12.1%, respectively, for warfarin and 7‐hydroxy warfarin, across the quality control standards (5, 10, 500, 1800 and 2000 ng/mL). Acceptable analytical recovery (>55%) was achieved with process efficiencies >41.5% and matrix effects <139.9% over the analytical range. Both analytes were stable in stock solution, autosampler, benchtop and three cycles of freeze–thaw with percent accuracy ≥90.2% and precision (percent relative standard deviation) ≤14%. The validated method was successfully applied to a pre‐clinical bioavailability study of crystalline and amorphous warfarin sodium formulations in SD rats.     

DNA interaction,cytotoxicity and molecular structure of cobalt complex of 4‐amino‐N‐(6‐chloropyridazin‐3‐yl)benzene sulfonamide in the presence of secondary ligand pyridine

Novel cobalt complex of 4‐amino‐N‐(6‐chloropyridazin‐3‐yl)benzene sulfonamide (sulfachloropyridazine) has been synthesized and characterized by elemental analysis, FT‐IR spectroscopy and magnetic susceptibility (VSM). Cobalt complex of Sulfachloropyridazine (Co‐SCP) crystallized in monoclinic space group P2₁/n with Z = 4. The structure is solved by direct method and refined to R = 0.099 for 4720 reflections with I ?4σ(I). The results of FT‐IR spectra suggest the binding of cobalt atom to the sulfonamide ligand which is in agreement with the crystal structure determination. In crystal structure, molecule is linked via, C‐H … π, C‐Cl … π and π … π intermolecular interactions. The computational studies like the optimization energy and root means square deviation compare with single crystal structure, frontier molecular orbital (Homo‐Lumo energy) and binding energy of the Co‐SCP has been carried out using DFT/B3LYP level of theory in gaseous phase. Hirshfeld surfaces and the 2D‐fingerprint analysis are performed to study the nature of interactions and their measurable contributions towards crystal packing. The interaction of the complex with DNA is investigated using viscosity measurement and absorption titration studies. The result shows the complex bind to DNA with intercalative mode with high DNA‐binding constant (K_b). Also, in vivo and in vitro cytotoxic studies are performed using S. pombe cells and brine shrimp lethality bioassay. DNA‐cleavage study shows better cleaving ability of the complex.     

Pressure controllable phase transition in MoTe2 by the interlayer band occupancy

High pressure can effectively control the phase transition of MoTe₂ in experiment, but the mechanism is still unclear. In this work, we show by first-principles calculations that the phase transition is suppressed and $1T^{\prime }$ phase becomes more stable under high pressure, which originates from the pressure-induced change of the interlayer band occupancies near the Fermi energy. Specifically, the interlayer states of $1T^{\prime }$ phase tend to be fully occupied under high pressure, while they keep partially occupied for the $T_d$ phase. The increase of the band occupancies makes the $1T^{\prime }$ phase more favorable in energy and prevents the structure changing from $1T^{\prime }$ to $T_d$ phase. Moreover, we also analyze the superconductivity under high pressure based on BCS theory by calculating the density of states and phonon spectra. Our results may shed some light on understanding the relationship between the interlayer band occupancy and crystal stability of MoTe₂ under high pressures.     

Insight into room-temperature catalytic oxidation of NO by CrO2(110): A DFT study

The first-principles DFT calculations together with microkinetic analysis reveal the complex catalytic mechanism of low-content NO oxidation on CrO₂(110) at room temperature. It quantitatively makes clear that CrO₂(110) can exhibit considerable activity with the Mars-van-Krevelen mechanism preferred, and the nitrate species serves as the key poisoning species.     

A dynamic free-entry oligopoly with sluggish entry and exit adjustments

We study a dynamic free-entry oligopoly with sluggish entry and exit of firms under general demand and cost functions. We show that the number of firms in a steady-state open-loop solution for a dynamic free-entry oligopoly is smaller than that at static equilibrium and that the number of firms in a steady-state memoryless closed-loop solution is larger than that in an open-loop solution.