Structures and energetics of complexation of metal ions with ammonia,water, and benzene: A computational study

Quantum chemical calculations have been performed at CCSD(T)/def2‐TZVP level to investigate the strength and nature of interactions of ammonia (NH₃), water (H₂O), and benzene (C₆H₆) with various metal ions and validated with the available experimental results. For all the considered metal ions, a preference for C₆H₆ is observed for dicationic ions whereas the monocationic ions prefer to bind with NH₃. Density Functional Theory–Symmetry Adapted Perturbation Theory (DFT‐SAPT) analysis has been employed at PBE0AC/def2‐TZVP level on these complexes (closed shell), to understand the various energy terms contributing to binding energy (BE). The DFT‐SAPT result shows that for the metal ion complexes with H₂O electrostatic component is the major contributor to the BE whereas, for C₆H₆ complexes polarization component is dominant, except in the case of alkali metal ion complexes. However, in case of NH₃ complexes, electrostatic component is dominant for s‐block metal ions, whereas, for the d and p‐block metal ion complexes both electrostatic and polarization components are important. The geometry (M⁺–N and M⁺–O distance for NH₃ and H₂O complexes respectively, and cation–π distance for C₆H₆ complexes) for the alkali and alkaline earth metal ion complexes increases down the group. Natural population analysis performed on NH₃, H₂O, and C₆H₆ complexes shows that the charge transfer to metal ions is higher in case of C₆H₆ complexes. © 2016 Wiley Periodicals, Inc.     

Conforming finite element methods for the von Kármán equations

In this paper, we consider canonical von Kármán equations that describe the bending of thin elastic plates defined on polygonal domains. A conforming finite element method is employed to approximate the displacement and Airy stress functions. Optimal order error estimates in energy, H ¹ and L ² norms are deduced. The results of numerical experiments confirm the theoretical results obtained.     

A Mixed Finite Element Method for Fourth Order Eigenvalue Problems

A new mixed finite element method for approximating eigenpairs of IV order elliptic eigenvalue problems with Dirichlet boundary conditions has been given. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Solvent extraction of Ni(II) from sulfate solutions with LIX 84I: flow-sheet for the separation of Cu(II), Ni(II) and Zn(II).

This paper reports on solvent-extraction studies of Ni(II) from sulfate solutions with LIX 84I (2-hydroxy-5-nonylacetophenoneoxime) as the extractant. The extraction of metal depends on the equilibrium pH of the aqueous phase and the extractant concentration. The transfer of metal follows a cation exchange-type mechanism: Ni2+ + 2HA --> NiA2 + 2H+. Extraction varies with the nature of the diluents. Temperature has no effect on the extraction of metal. The extraction behavior of associated metals clearly demonstrates the application of LIX 84I as the extractant for the separation of Cu(II), Ni(II) and Zn(II). Based on the results, a flow sheet of the process was developed.     

A qualocation method for Burgers’ equation

In this paper, a qualocation method for the one-dimensional Burgers’ equation is proposed. A semidiscrete scheme along with optimal error estimates is discussed. Results of a numerical experiment performed support the theoretical results.     

The unusual formation of methyl α-(5,6-dimethoxycarbonyl-2,3-dimethoxyazepin-7-ylidene)-α-[5-methoxycarbonyl-2,3-dimethoxypyrid-6-yl)acetate during the pyrolysis of “Azido-meta-hemipinate”: First example of a reaction involving a concomitant ring expansion and ring extrusion

The ortho methoxycarbonyl substituent constitutes a sole exception in the ring closure reactions of ortho substituted aryl azides, as it provides no rate acceleration to this reaction. Pyrolysis of “azido-meta-hemipinate”, an aryl azide containing such a substituent, led us to the title compound, a new azepinylidene-pyridylacetic ester, whose structure has been established unambiguously by a single crystal X-ray diffraction study. This is the first report of a reaction involving both a ring expansion to an azaheptafulvalene and a ring extrusion to a pyridyl ring residue.     

Finite volume element method for the incompressible miscible displacement problems in porous media

We present the finite volume element method (FVEM) for incompressible miscible displacement problems in porous media. Optimal error estimates in L^∞(L²) are derived for velocity and concentration. Numerical experiments are also presented. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

First principles study and database analyses of structural preferences for sodium ion (Na+) solvation and coordination

Extensive computations were performed on aqueous clusters of monovalent sodium cation [Na⁺(H₂O) _n ; (n = 1–20)] using MP2/cc-pVTZ and density functional theory. The structure, energy, and coordination number (CN) preference of a large number of competing conformations of different complexes have been explored. For complexes up to n = 12, the CN 4 is most preferred while 5, 6 CNs are favored in case of larger complexes containing up to 20 water molecules. These results are in very good agreement with experimental observations. The strength of hydrogen bonding among the waters coordinated to the Na⁺ ion is found to play a major role in the stability of the complexes. The varying preferences for CN of Na⁺ ion were explored by screening two important databases: Protein Databank and Cambridge Structural Database. A linear correlation is observed between the M (Metal)–O distance and the charge on metal ion in complex with the increase in CN of metal ion.