Reactions of bromine and chlorine with osmium hexafluoride

Osmium hexafluoride combines with bromine to form Br₂OsF₆. Solutions of OsF₆ in liquid chlorine are strongly blue or blue violet in colour, and charge transfer interactions are indicated.     

Oxidation studies—V

Oxidation of light and heavy water by peroxy disulphate was studied at 60–70° C. The acid independent and acid dependent rate constants and respective ΔE values were computed. An attempt is made to explain the kinetic isotopic effect observed. A probable mechanism is proposed.     

Synthesis, spectral characterization, catalytic and antibacterial studies of new Ru(III) Schiff base complexes containing chloride/bromide and triphenylphosphine/arsine as co-ligands

A new Ru(III) Schiff base complexes of the type [RuX(EPh₃)L] (X = Cl/Br; E = P/As; L = dianion of the Schiff bases were derived by the condensation of 1,4-diformylbenzene with o-aminobenzoic acid/o-aminophenol/o-aminothiophenol in the 1:2 stoichiometric ratio) have been synthesized from the reactions of [RuX₃(EPh₃)₃] with appropriate Schiff base ligands in benzene in the 2:1 stoichiometric ratio. The new complexes have been characterized by analytical, spectral (IR, electronic, ¹H, ¹³C NMR and ESR), magnetic moment and electrochemical studies. An octahedral structure has been tentatively proposed for all these new complexes. All the new complexes have been found to be better catalyst for the oxidation of alcohols using molecular oxygen as co-oxidant at ambient temperature and aryl–aryl coupling reactions. These complexes were also subjected to antibacterial activity studies against Escherichia coli, Aeromonas hydrophilla and Salmonella typhi.     

Understanding hydrogen scrambling and infrared spectrum of bare CH5+ based on ab initio simulations

A comprehensive study of the properties of protonated methane obtained from ab initio molecular dynamics simulations is presented. Comparing computed infrared spectra to the measured one gives further support to the high fluxionality of bare CH(5)(+). The computational trick to partially freezing out large-amplitude motion, in particular hydrogen scrambling and internal rotation of the H(2) moiety, leads to an understanding of the measured IR spectrum despite the underlying rapid hydrogen scrambling motion that interconverts dynamically structures of different symmetry and chemical bonding pattern. In particular, the fact that C-H stretching modes involving the carbon nucleus and those protons that form the H(2) moiety and the CH(3) tripod, respectively, result in distinct peaks is arguably experimental support for three-center two-electron bonding being operative at experimental conditions. It is proposed that hydrogen scrambling is associated with the softening of a mode that involves the bending of the H(2) moiety relative to the CH(3) tripod, which characterizes the C(s) ground-state structure. The potential energy surface that is mapped on to a two dimensional subspace of internal coordinates provides insight into the dynamical mechanism for exchange of hydrogens between CH(3) tripod and the three-center bonded H(2) moiety that eventually leads to full hydrogen scrambling.     

Study of the reactions of pyridinium poly(hydrogen fluoride) with some ternary oxides

The products of the reaction of pyridinium poly(hydrogen fluoride), PPHF, with KIO₃, Na₂SnO₃, NaBiO₃, K₂CrO₄, Na₂MoO₄ and Na₂WO₄ were KIO₂F₂; Na₂SnF₆; NaHF₂, BiF₃; K₃CrF₆, KHF₂, (PyH)₃CrF₆; NaHF₂, (PyH)₂MoO₂F₄·2NaHF₂; and (PyH)₂WO₂F₄·2NaHF₂, respectively, while KClO₃, KBrO₃ and KIO₄ react with complete decomposition to form KHF₂ as the fluorinated product. This differential reactivity and mode of reaction has been discussed in terms of the oxidation state of the central atom, the nature and strength of the bonds and the complex behaviour of the formed intermediate or fluorinated products that undergo complexation or solvation with pyridine and/or hydrogen fluoride.     

Macroreticular Phenolic Cationites

Macroreticular cation exchangers can be prepared by polymerizing sulfonated phenols with formaldehyde under acidic conditions. The resins are highly porous with large surface areas. Their properties compare well with those based on styrene and divinylbenzene copolymers.     

Mathematical and physical aspects of controlling the exact solutions of the 3D Gross-Pitaevskii equation

The possibility of the decomposition of the three-dimensional (3D) Gross-Pitaevskii equation (GPE) into a pair of coupled Schrödinger-type equations, is investigated. It is shown that, under suitable mathematical conditions, it is possible to construct the exact controlled solutions of the 3D GPE from the solutions of a linear 2D Schrödinger equation coupled with a 1D nonlinear Schrödinger equation (the transverse and longitudinal components of the GPE, respectively). The coupling between these two equations is the functional of the transverse and the longitudinal profiles. The applied method of nonlinear decomposition, called the controlling potential method (CPM), yields the full 3D solution in the form of the product of the solutions of the transverse and longitudinal components of the GPE. It is shown that the CPM constitutes a variational principle and sets up a condition on the controlling potential well. Its physical interpretation is given in terms of the minimization of the (energy) effects introduced by the control. The method is applied to the case of a parabolic external potential to construct analytically an exact BEC state in the form of a bright soliton, for which the quantitative comparison between the external and controlling potentials is presented.     

Correlation between extrinsic magnetoresistance and electroresistance in La0.6Pb0.4MnO3 thin films as revealed from current-voltage and ferromagnetic resonance studies

We have investigated magnetoresistance (MR) and electroresistance (ER) of well characterized La_0.6Pb_0.4MnO₃ (LPMO) films having two different crystallinity (i) (00l) oriented single-crystalline, SC, i.e. without any grain boundaries, and (ii) nanocrystalline, NC, with an average grain size of 17 nm. Both MR and ER were remarkably different for the two films, that is, (i) NC films exhibited a highest MR of ∼100% near the metal-insulator transition temperature; while for SC films the MR was in the range of 40-60%, (ii) NC films exhibited a finite ER, which increased monotonically with decreasing temperature; while in SC films ER was completely absent. Using current-voltage characteristic and ferromagnetic resonance studies we demonstrate that both enhanced MR and ER in NC films are extrinsic in nature and originate due to the presence of spin glassy grain boundaries.