Prediction of 195Pt NMR chemical shifts of dissolution products of H2[Pt(OH)6] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

¹⁹⁵Pt NMR chemical shifts of octahedral Pt(IV) complexes with general formula [Pt(NO₃)_n(OH)_{6 ? n}]^2?, [Pt(NO₃)_n(OH₂)_{6 ? n}]^{4 ? n} (n = 1–6), and [Pt(NO₃)_{6 ? n ? m}(OH)_m(OH₂)_n]^{?2 + n ? m} formed by dissolution of platinic acid, H₂[Pt(OH)₆], in aqueous nitric acid solutions are calculated employing density functional theory methods. Particularly, the gauge‐including atomic orbitals (GIAO)‐PBE0/segmented all‐electron relativistically contracted–zeroth‐order regular approximation (SARC–ZORA)(Pt) ∪ 6–31G(d,p)(E)/Polarizable Continuum Model computational protocol performs the best. Excellent second‐order polynomial plots of δ_calcd(¹⁹⁵Pt) versus δ_exptl(¹⁹⁵Pt) chemical shifts and δ_calcd(¹⁹⁵Pt) versus the natural atomic charge Q_Pt are obtained. Despite of neglecting relativistic and spin orbit effects the good agreement of the calculated δ ¹⁹⁵Pt chemical shifts with experimental values is probably because of the fact that the contribution of relativistic and spin orbit effects to computed σ^{iso 195}Pt magnetic shielding of Pt(IV) coordination compounds is effectively cancelled in the computed δ ¹⁹⁵Pt chemical shifts, because the relativistic corrections are expected to be similar in the complexes and the proper reference standard used. To probe the counter‐ion effects on the ¹⁹⁵Pt NMR chemical shifts of the anionic [Pt(NO₃)_n(OH)_{6 ? n}]^2? and cationic [Pt(NO₃)_n(OH₂)_{6 ? n}]^{4 ? n} (n = 0–3) complexes we calculated the ¹⁹⁵Pt NMR chemical shifts of the neutral (PyH)₂[Pt(NO₃)_n(OH)_{6 ? n}] (n = 1–6; PyH = pyridinium cation, C₅H₅NH⁺) and [Pt(NO₃)_n(H₂O)_{6 ? n}](NO₃)_{4 ? n} (n = 0–3) complexes. Counter‐anion effects are very important for the accurate prediction of the ¹⁹⁵Pt NMR chemical shifts of the cationic [Pt(NO₃)_n(OH₂)_{6 ? n}]^{4 ? n} complexes, while counter‐cation effects are less important for the anionic [Pt(NO₃)_n(OH)_{6 ? n}]^2? complexes. The simple computational protocol is easily implemented even by synthetic chemists in platinum coordination chemistry that dispose limited software availability, or locally existing routines and knowhow. Copyright © 2016 John Wiley & Sons, Ltd.     

Viscosity solutions to a parabolic inhomogeneous equation associated with infinity Laplacian

We obtain the existence and uniqueness results of viscosity solutions to the initial and boundary value problem for a nonlinear degenerate and singular parabolic inhomogeneous equation of the form ut- ΔN∞u = f,where ΔN∞denotes the so-called normalized infinity Laplacian given by ΔN∞u =1|Du|2 D2 uD u, Du.     

MHD flow and heat transfer of a hybrid nanofluid past a permeable stretching/shrinking wedge

The steady flow and heat transfer of a hybrid nanofluid past a permeable stretching/shrinking wedge with magnetic field and radiation effects are studied. The governing equations of the hybrid nanofluid are converted to the similarity equations by techniques of the similarity transformation. The bvp4c function that is available in MATLAB software is utilized for solving the similarity equations numerically. The numerical results are obtained for selected different values of parameters. The results discover that two solutions exist, up to a certain value of the stretching/shrinking and suction strengths. The critical value in which the solution is in existence decreases as nanoparticle volume fractions for copper and wedge angle parameter increase. It is also found that the hybrid nanofluid enhances the heat transfer rate compared with the regular nanofluid. The reduction of the heat transfer rate is observed with the increase in radiation parameter. The temporal stability analysis is performed to analyze the stability of the dual solutions, and it is revealed that only one of them is stable and physically reliable.     

Stochastic and upscaled analytical modeling of fines migration in porous media induced by low-salinity water injection

Fines migration induced by injection of low-salinity water(LSW) into porous media can lead to severe pore plugging and consequent permeability reduction. The deepbed filtration(DBF) theory is used to model the aforementioned phenomenon, which allows us to predict the effluent concentration history and the distribution profile of entrapped particles. However, the previous models fail to consider the movement of the waterflood front. In this study, we derive a stochastic model for fines migration during LSW flooding, in which the Rankine-Hugoniot condition is used to calculate the concentration of detached particles behind and ahead of the moving water front. A downscaling procedure is developed to determine the evolution of pore-size distribution from the exact solution of a large-scale equation system. To validate the proposed model,the obtained exact solutions are used to treat the laboratory data of LSW flooding in artificial soil-packed columns. The tuning results show that the proposed model yields a considerably higher value of the coefficient of determination, compared with the previous models, indicating that the new model can successfully capture the effect of the moving water front on fines migration and precisely match the effluent history of the detached particles.     

Rotational flow of Oldroyd-B nanofluid subject to Cattaneo-Christov double diffusion theory

A nanofluid is composed of a base fluid component and nanoparticles, in which the nanoparticles are dispersed in the base fluid. The addition of nanoparticles into a base fluid can remarkably improve the thermal conductivity of the nanofluid, and such an increment of thermal conductivity can play an important role in improving the heat transfer rate of the base fluid. Further, the dynamics of non-Newtonian fluids along with nanoparticles is quite interesting with numerous industrial applications. The present predominately predictive modeling studies the flow of the viscoelastic Oldroyd-B fluid over a rotating disk in the presence of nanoparticles. A progressive amendment in the heat and concentration equations is made by exploiting the Cattaneo-Christov heat and mass flux expressions. The characteristic of the Lorentz force due to the magnetic field applied normal to the disk is studied. The Buongiorno model together with the Cattaneo-Christov theory is implemented in the Oldroyd-B nanofluid flow to investigate the heat and mass transport mechanism. This theory predicts the characteristics of the fluid thermal and solutal relaxation time on the boundary layer flow. The von K′arm′an similarity functions are utilized to convert the partial differential equations(PDEs) into ordinary differential equations(ODEs). A homotopic approach for obtaining the analytical solutions to the governing nonlinear problem is carried out. The graphical results are obtained for the velocity field, temperature, and concentration distributions. Comparisons are made for a limiting case between the numerical and analytical solutions, and the results are found in good agreement. The results reveal that the thermal and solutal relaxation time parameters diminish the temperature and concentration distributions, respectively. The axial flow decreases in the downward direction for higher values of the retardation time parameter. The impact of the thermophoresis parameter boosts the temperature distribution.     

Multifunctional material Bi4Ge3O12: thermodynamic properties

Thermodynamic characteristics of a single crystal of bismuth orthogermanate (Bi₄Ge₃O₁₂), which are necessary to improve device portfolio, have been studied. It has been shown that bismuth orthogermanate is thermodynamically stable against decomposition into binary oxides at 50 °C, which gives us grounds to consider this compound promising for various applications.     

Multiple bright and dark soliton solutions in three component spinor Bose-Einstein condensates

We investigate a quasi one dimensional spin-1 Bose-Einstein Condensates (BEC) in the absence of an external confinement governed by a system of three coupled Gross-Pitaevskii (GP) equation. Based on the Lax-pair, we construct one soliton solution employing gauge transformation method. In addition, the multiple bright and dark soliton solutions are obtained by properly choosing amplitude dependent parameter in the Lax-pair. The results of the paper emphasizes the richness in the structure of soliton solutions admitted by the spin components, a phenomenon which has never been brought out to the fore. We have also extended the gauge transformation method to generate two soliton solutions.     

2个位势的Ablowitz-Ladik等谱方程的Complexiton解

借助双Casoratian技巧和构造双Wronski行列式元素的矩阵方法,求出2个位势的Ablowitz-Ladik等谱方程的Complexiton解和周期解,并通过将矩阵取成不同的组合类型,进而分别得到该方程具有双Casorati行列式形式的新解,即Complexiton解与类有理解的混合解、Complexiton解与Matveev解的混合解.     

椰心叶甲虫综合防治脉冲动力学模型的周期解

椰心叶甲虫是棕榈科植物最主要的害虫之一.论文针对两类寄生蜂攻击椰心叶甲虫不同年龄阶段的特点,建立了阶段结构的脉冲定期喷洒药物和释放天敌的综合防治模型.通过重合度理论和分析工具,证明了该模型周期解的存在性,给出了周期解存在的充分条件,并通过数值模拟验证了理论结果的有效性.