The effect of charge on the dihydrogen storage capacity of Sc2–C6H6

The effect of charge on the dihydrogen storage capacity of Sc₂–C₆H₆ has been investigated at B3LYP-D3/6-311G(d,p) level. The neutral system Sc₂–C₆H₆ can store 8H₂ with gravimetric density of 8.76 wt %, and one H₂ dissociates and bonds atomically on the scandium atom. The adsorption of 8H₂ on Sc₂–C₆H₆ is energetically favorable below 155 K. The atom-centered density matrix propagation (ADMP) molecular dynamics simulations show that Sc₂–C₆H₆ can adsorb 3H₂ within 1000 fs at 300K. Compared with Sc₂–C₆H₆, the charged systems can adsorb more hydrogen molecules with higher gravimetric density, and all the H₂ are adsorbed in the molecular form. The gravimetric densities of Sc₂–C₆H₆⁺ and Sc₂–C₆H₆²⁺ are 9.75 and 10.71 wt%. Moreover, the maximum adsorption of charged systems are favorable in wider temperature range. Most importantly, the ADMP-MD simulations indicate that Sc₂–C₆H₆²⁺ can adsorb 6 hydrogen molecules within 1000 fs at 300K. It can be found that the gravimetric density (6.72 wt%) of Sc₂–C₆H₆²⁺ still exceeds the target of US Department of Energy (DOE) under ambient conditions.     

Bond characteristics,vibrational spectrum and optimized microwave dielectric properties of chemically substituted NdNbO4

Coordination chemistry, bond state and vibrational spectrum of co-substituted microwave dielectric NdNb_1-x(Zr_0.5W_0.5)_xO₄ ceramics (x = 0.01∼0.05) were investigated. Raman spectra and XRD refinement showed a solid solution was formed. The compressed and elongated chemical bonds are responsible for the variations of crystal parameters and cell volume. Calculated chemical bond parameters indicated bond covalency, lattice energy and Nb-site bond energy act on the fluctuations of the permittivity, quality factor and temperature coefficient, respectively. Meanwhile, the infrared vibrational spectrum is fitted to quantify the contributions of observed IR mode to the intrinsic loss. Compact ceramic possesses excellent properties: ε_r ∼ 19.2, Q × f ∼ 55282 GHz and τ_f ∼ -11.36 ppm/°C with x = 0.04, at 1250°C.     

OWL‐based acquisition and editing of computer‐interpretable guidelines with the CompGuide editor

Computer‐Interpretable Guidelines (CIGs) are the dominant medium for the delivery of clinical decision support, given the evidence‐based nature of their source material. Therefore, these machine‐readable versions have the ability to improve practitioner performance and conformance to standards, with availability at the point and time of care. The formalisation of Clinical Practice Guideline knowledge in a machine‐readable format is a crucial task to make it suitable for the integration in Clinical Decision Support Systems. However, the current tools for this purpose reveal shortcomings with respect to their ease of use and the support offered during CIG acquisition and editing. In this work, we characterise the current landscape of CIG acquisition tools based on the properties of guideline visualisation, organisation, simplicity, automation, manipulation of knowledge elements, and guideline storage and dissemination. Additionally, we describe the CompGuide Editor, a tool for the acquisition of CIGs in the CompGuide model for Clinical Practice Guidelines that also allows the editing of previously encoded guidelines. The Editor guides the users throughout the process of guideline encoding and does not require proficiency in any programming language. The features of the CIG encoding process are revealed through a comparison with already established tools for CIG acquisition.     

In situ Raman spectroscopic study towards the growth and excellent HER catalysis of Ni/Ni(OH)2 heterostructure

The electrochemical water splitting to produce H₂ in high efficiency with earth-abundant-metal catalysts remains a challenge. Here, we describe a simple “cyclic voltammetry + ageing” protocol at room temperature to activate Ni electrode (AC-Ni/NF) for hydrogen evolution reaction (HER), by which Ni/Ni(OH)₂ heterostructure is formed at the surface. In situ Raman spectroscopy reveals the gradual growth of Ni/Ni(OH)₂ heterostructure during the first 30 min of the aging treatment and combined with polarization measurements, it suggests a positive relation between the Ni/Ni(OH)₂ amount and HER performance of the electrode. The obtained AC-Ni/NF catalyst, with plentiful Ni–Ni(OH)₂ interfaces, exhibits remarkable performance towards HER, with the low overpotential of only 30 mV at a H₂-evolving current density of 10 mA/cm² and 153 mV at 100 mA/cm², as well as a small Tafel slope of 46.8 mV/dec in 1 M KOH electrolyte at ambient temperature. The excellent HER performance of the AC-Ni/NF could be maintained for at least 24 h without obvious decay. Ex situ experiments and in situ electrochemical-Raman spectroscopy along with density functional theory (DFT) calculations reveal that Ni/Ni(OH)₂ heterostructure, although partially reduced, can still persist during HER catalysis and it is the Ni–Ni(OH)₂ interface reducing the energy barrier of H1 adsorption thus promoting the HER performance.     

Crystallographic characteristics and microwave dielectric properties of Ni-modified MgTa2O6 ceramics

Ni²⁺ modified MgTa₂O₆ ceramics with a trirutile phase and space group P4₂/mnm were obtained. The correlations between crystallographic characteristics and microwave dielectric performance of MgTa₂O₆ ceramics were systematically studied based on the chemistry bond theory (PVL theory) for the first time. The results indicate that the introduction of Ni²⁺ causes a change in polarizability and the Mg–O bond ionicity, which contributes to the variation of dielectric constant. Moreover, the lattice energy, and packing fraction, full width at half maximum of the Raman peak of Ta–O bond, as the quantitative characterization of crystallographic parameters, regulate the dielectric loss of MgTa₂O₆ ceramics in GHz frequency band. In addition, the study of sintering behavior shows that the densification and micromorphology are the crucial factors affecting the microwave dielectric performance. Typically, Ni²⁺ doping on the A-site of MgTa₂O₆ can effectively promote the Q × f values to 173,000 GHz (at 7.43 GHz), which ensures its applicability in 5G communication technology.     

Torsional statics of two-dimensionally functionally graded microtubes

A size-dependent governing equation is derived to investigate the torsional static behaviors of two-dimensionally functionally graded microtubes based on the modified couple stress theory. The shear modulus is assumed to vary along the tube’s length direction according to an exponential distribute function, and varies along the tube’s radius direction according to a power-law function. A generalized differential quadrature method is developed to determine the rotational angle and shear stresses. Some illustrative examples are given to investigate the effects of applied torques, the length scale parameter and various material compositions on the torsional angle and shear stresses.     

Theoretical kinetic study of the reaction between dimethyl disulfide and OH radicals

The potential energy profile of the reaction between dimethyl disulfide and OH^? radicals is explored by utilizing ab initio and hybrid meta density functional theory methods. Having the energies and structural data of the stationary points, statistical rate theories, such as transition state theory and variable reaction coordinate-transition state theory, are employed to compute the overall rate constants, and discuss the mechanism and product channels. On the basis of the calculations, the overall rate coefficient is predicted to be 2.49?×?10^?10?cm³?molecule^?1?s^?1 at 298?K. It is found that in the most favorable pathway, the reaction proceeds via formation of the relatively unstable intermediate CH₃S^?(OH)SCH₃ decomposing rapidly to yield CH₃S^?+CH₃SOH.     

Ab initio calculations of the NO2 fission for CL-20 conformers

NO₂ fission is regarded to be the most important initial decomposition process of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20). In this study, four CL-20 conformers based on the ε-CL-20 were obtained after the optimization at m062x/cc-pvtz level, and the bond length, bond order and bond dissociation energy of the N-N bonds were examined to investigate the stability of these bonds. In addition, the rate constants and activation energy of the NO₂ fission were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that N-N bonds in the case of pseudo-equatorial and axial of nitro groups are the most stable and the least stable, respectively, by evaluating the bond length, bond order and minimum energy path (MEP). The NO₂ fission rate constants are affected by not only the stability of N-N bonds but also the repulsion forces from the other nitro groups, and the fission process for pseudo-equatorial positioning of nitro groups is easier to be accelerated due to the increase of the repulsion forces. The decomposition of CL-20 conformer may mainly originate from the fission of the pseudo-equatorial positioning of nitro groups, especially for CL-20 III conformer because of the significant low activation energy.