Hydration structure of Na+ and K+ from ab initio molecular dynamics based on modern density functional theory

Molecular dynamics (Born–Oppenheimer) simulations based on density functional theory have been carried out to investigate the solvation structure of monovalent Na⁺ and K⁺ cations in water under ambient conditions. Four recently proposed van der Waals (vdW) density functionals (LMKLL, DRSLL, DRSLL-PBE, DRSLL-optB88), the semiempirical vdW method of Grimme (BLYP-D3) and conventional gradient-corrected (GGA-BLYP) density functionals are applied in order to evaluate their accuracy in describing the hydration structure of alkali metal ions. Theoretical results are compared to available experimental data. Our results indicate that addition of corrections accounting for dispersion forces significantly improves the agreement between predicted and measured coordination numbers for both Na⁺ and K⁺ cations. Analysis of radial distribution functions brings further support to the notion that the choice of the generalised gradient approximation density functional impacts crucially on the computed structural properties. DRSLL-optB88 and BLYP-D3 provide the best agreement with experiment.     

Analysis of dispersions of coupled asymmetric subwavelength-diameter wires

We propose a novel waveguide based on a structure of coupled asymmetric subwavelength-diameter wires to realize a high negative dispersion. The waveguide consists of an optical nanofiber and a GaAs nanowire. The properties of the supermodes are calculated using finite elements method. The results show that the symmetric supermode in the coupled structure can exhibit a giant negative dispersion up to −4.5 × 10⁶ ps/nm/km.     

Effective parameter extraction of 3D metamaterial arrays via first-principles homogenization theory

In this paper, the effective parameters of diverse single-negative bulk structures are extracted in terms of first-principles homogenization techniques. Each metamaterial unit-cell is initially considered to be an electrically small scatterer, and under this assumption, its polarizabilities are derived via a dynamic approach. Also, the wavenumber of a normally incident propagating plane wave through the aforementioned single-negative structures is obtained by means of several algorithms. The retrieved polarizabilities of a single scatterer and the wavenumber of the periodic medium are, finally, incorporated in the homogenization formulas to compute the desired effective parameters. Numerical verification addressing the analysis of two different resonators and comparisons with the results of a popular homogenization method, reveals the merits of the proposed formulation and proves its overall efficiency.     

Approximate Theoretical Study on the Characteristic of a Femtosecond KLM Laser

The conclusion that the pulse-width is proportional to the square root of the third order dispersion coefficient is obtained by using the modified higher-order nonlinear Schr?dinger equation with concurrent actions of third order dispersion and self-steepen effect when a femtosecond pulse propagates steadily in a laser. This result is in agreement with the experimental result. Besides, the action of second order dispersion term is also discussed in the realization of mode locking process of a laser.     

Thermal dispersion driven by the spontaneous imbibition process

In this work, we have theoretically analyzed the thermal dispersion process under the influence of the spontaneous imbibition of a liquid trapped in a capillary element, considering the presence of a uniform temperature gradient. The capillary element is represented by a porous medium which is initially found at temperature T₀ and pressure P₀. Suddenly, the lower part of the porous medium touches a liquid reservoir at temperature T_l and pressure P₀. This contact between both phases, in turn causes spontaneously the imbibition process. Using a one-dimensional formulation of the average conservation laws, we derive the corresponding nondimensional momentum and energy equations. The numerical solutions permit us to evaluate the position and velocity of the imbibition front as well as the temperature profiles and Nusselt numbers. The above results are shown by taking into account the influence of three dimensionless parameters: the ratio of the characteristic thermal time to the characteristic imbibition time, β, the ratio of the hydrostatic head of the imbibed liquid to the characteristic pressure difference for the imbibition front, α, and the ratio of the dispersive thermal diffusivity to the effective thermal diffusivity of the medium, Ω. The predictions show that temperature profiles and the heat transfer process are strongly dependent on thermal dispersion effects, indicating a clear deviation in comparison with the case of Ω = 0 that represents the absence of the thermal dispersion.     

Nonlinear Comparison of High-order and Optimized Finite-difference Schemes

The effect of reducing the formal order of accuracy of a finite-difference scheme in order to optimize its high-wavenumber performance, is investigated using the 1-D nonlinear unsteady inviscid Burgers' equation. Both explicit and compact schemes are compared to schemes wilh various levels of optimization. Results are given for the absolute and L2 errors as a function of time. It is found that the benefits of optimization do carry over into nonlinear applications.     

Simultaneous determination and qualitative analysis of six types of components in Naoxintong capsule by miniaturized matrix solid‐phase dispersion extraction coupled with ultra high‐performance liquid chromatography with photodiode array detection and quadrupole time‐of‐flight mass spectrometry

A simple and effective sample preparation process based on miniaturized matrix solid‐phase dispersion was developed for simultaneous determination of phenolic acids (gallic acid, chlorogenic acid, ferulic acid, 3,5‐dicaffeoylqunic acid, 1,5‐dicaffeoylqunic acid, rosmarinic acid, lithospermic acid, and salvianolic acid B), flavonoids (kaempferol‐3‐O‐rutinoside, calycosin, and formononetin), lactones (ligustilide and butyllidephthalide), monoterpenoids (paeoniflorin), phenanthraquinones (cryptotanshinone), and furans (5‐hydroxymethylfurfural) in Naoxintong capsule by ultra high‐performance liquid chromatography. The optimized condition was that 25 mg Naoxintong powder was blended homogeneously with 100 mg Florisil PR for 4 min. One milliliter of methanol/water (75:25, v/v) acidified by 0.05% formic acid was selected to elute all components. It was found that the recoveries of the six types of components ranged from 61.36 to 96.94%. The proposed miniaturized matrix solid‐phase dispersion coupled with ultra high‐performance liquid chromatography was successfully applied to simultaneous determination of the six types of components in Naoxintong capsules. The results demonstrated that the proposed miniaturized matrix solid‐phase dispersion coupled with ultra high‐performance liquid chromatography could be used as an environmentally friendly tool for the extraction and determination of multiple bioactive components in natural products.     

Electron inelastic mean free path (IMFP) values of Kapton,polyethylene (PE), polymethylmethacrylate (PMMA), polystyrene (PS) and polytetrafluoroethylene (PTFE) measured with elastic peak electron spectroscopy (EPES)

Elastic peak electron spectroscopy (EPES) was employed to measure the inelastic mean free path (IMFP) for energies between 500 and 1600 eV for five insulating organic compounds: Kapton, polyethylene (PE), poly(methyl methacrylate) (PMMA), polystyrene (PS) and polytetrafluoroethylene (PTFE). A Ni and a Si sample were used as reference materials to avoid measurement of the elastic reflection coefficient in absolute units. Correction of experimental elastic peak intensities for surface excitations was performed which turned out to be essential. The results are compared with recent evaluations of optical constants to yield the IMFP in the literature giving satisfactory agreement, with deviations generally below 20%. Investigation of the kinematics in an electron reflection experiment shows that the dispersion coefficient used in REELS data analysis cannot be identified with the true plasmon dispersion.     

异戊橡胶中填料的絮凝及其对性能的影响

针对硫化过程对异戊橡胶中的填料絮凝及其性能的影响等问题, 通过改变硫化温度和硫化时间, 对比研究了炭黑、 白炭黑、 炭黑/白炭黑混合填料体系中的填料絮凝过程, 比较其动、 静态性能等的变化. 为了分析交联网络在填料絮凝过程中的贡献, 对比了工艺相同的含硫与不含硫胶料在不同温度和时间下的絮凝过程. 在含硫体系中, 佩恩效应主要来自于填料网络和橡胶网络的贡献; 而在不含硫体系中, 佩恩效应主要来自于填料网络的贡献. 研究结果表明, 橡胶网络的形成在一定程度上限制了填料的絮凝, 因此, 随温度升高, 含硫体系的佩恩效应减小, 而无硫体系的佩恩效应逐渐增加或先减小后增加. 随时间延长, 含硫胶料和无硫胶料的佩恩效应均增加, 但机制有所不同. 其中含硫胶料主要来自于交联网络的形成, 而无硫胶料主要来自于填料的絮凝. 絮凝动力学研究表明, 快速絮凝发生在较短的时间范围内, 在长时间范围内絮凝开始变慢但并不会停止, 且在较低温度(60 ℃)下絮凝仍会发生. 此外, 高温和长时间热处理导致材料的拉伸性能出现下降, 但动态疲劳性能有所增强.     

Hydrocarbon Soluble Alkali-Metal-Aluminium Hydride Surrog[ATES]

A series of group 1 hydrocarbon-soluble donor free aluminates [AM(^tBuDHP)(TMP)Al(ⁱBu)₂] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2-^tBuC₅H₅N)AM)] containing a surrogate hydride (sp³ C−H) with [(ⁱBu)₂Al(TMP)]. These aluminates have been characterised by X-ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier alkali metal aluminates exist as polymeric chains propagated by non-covalent interactions between the alkali metal cations and the alkyldihydropyridyl units. Solvates [(THF)Li(^tBuDHP)(TMP)Al(ⁱBu)₂] and [(TMEDA)Na(^tBuDHP)(TMP)Al(ⁱBu)₂] have also been crystallographically characterised. Theoretical calculations show how the dispersion forces tend to increase on moving from Li to Rb, as opposed to the electrostatic forces of stabilization, which are orders of magnitude more significant. Having unique structural features, these bimetallic compounds can be considered as starting points for exploring unique reactivity trends as alkali-metal-aluminium hydride surrog[ATES].