Water reorientation dynamics in the first hydration shells of F- and I-

Molecular dynamics and analytic theory results are presented for the reorientation dynamics of first hydration shell water molecules around fluoride and iodide anions. These ions represent the extremes of the (normal) halide series in terms of their size and conventional structure-making and -breaking categorizations. The simulated reorientation times are consistent with NMR and ultrafast IR experimental results. They are also in good agreement with the theoretical predictions of the analytic Extended Jump Model. Analysis through this model shows that while sudden, large amplitude jumps (in which the reorienting water exchanges hydrogen-bond partners) are the dominant reorientation pathway for the I(-) case, they are comparatively less important for the F(-) case. In particular, the diffusive reorientation of an intact F(-)···H(2)O hydrogen-bonded pair is found to be most important for the reorientation time, a feature related to the greater hydrogen-bond strength for the F(-)···H(2)O pair. The dominance of this effect for e.g. multiply charged ions is suggested.     

Enantioselective Arylation of N‐Tosylimines by Phenylboronic Acid Catalysed by a Rhodium/Diene Complex: Reaction Mechanism from Density Functional Theory

A DFT study of the reaction mechanism of the rhodium‐catalysed enantioselective arylation of (E)‐N‐propylidene‐4‐methyl‐benzenesulfonamide by phenylboronic acid [Lin et al J. Am. Chem. Soc.­ 2011 , 133, 12394] is reported. The catalyst ([{Rh(OH)(diene)}₂]) includes a chiral diene ligand and the reaction is conducted in 1,4‐dioxane in the presence of drying agents (4 Å molecular sieves). Because phenylboronic acid is in equilibrium with phenylboroxin and water under the reaction conditions, three catalytic cycles are proposed that differ in the way the transmetallation and the release of the product are brought about, depending on the availability of phenylboronic acid, water and boroxin in the reaction medium. Based on computations, a new mechanism for the title reaction is proposed, in which phenylboronic acid plays the double role of “aryl source” and proton donor. This path does not require the presence of adventitious water molecules, in keeping with a reaction conducted in a dry medium. Comparisons with the generally accepted mechanism for arylation of enones proposed by Hayashi and co‐workers (J. Am. Chem. Soc.­ 2002 , 124, 5052) show that the latter mechanism is less favourable and is not expected to operate in the case of the N‐tosylimine substrate considered herein. Finally, the possibility that phenylboroxin is the aryl source has also been investigated, but is not found to be competitive.     

Full coverage film cooling using compound angle

An experimental and numerical study is carried out on a cooling film issuing from a multiperforated wall of a simplified combustor. The objectives of this work are to achieve a better understanding of the dynamics of the film and to construct an experimental database on a simplified geometry in order to test numerical models. A parametric study of film cooling efficiency based on the direction of the cooling air injection is presented and shows that a swirling injection greatly enhances the cooling efficiency. As accounting for multiperforated walls in numerical simulations cannot be done at the jets scale because of computing resources, in this article are presented RANS computations performed using a uniform boundary condition to provide the injection of coolant. Two injection models are applied on this boundary and numerical results are compared to experimental data in the recovery region. The standard model is shown to be totally inappropriate while the multiperforation model delivers promising results although some weaknesses appear very close to the wall. To cite this article: B. Michel et al., C. R. Mecanique 337 (2009).     

Selective binding of O2 over N2 in a redox-active metal-organic framework with open iron(II) coordination sites

The air-free reaction between FeCl(2) and H(4)dobdc (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) in a mixture of N,N-dimethylformamide (DMF) and methanol affords Fe(2)(dobdc)·4DMF, a metal-organic framework adopting the MOF-74 (or CPO-27) structure type. The desolvated form of this material displays a Brunauer-Emmett-Teller (BET) surface area of 1360 m(2)/g and features a hexagonal array of one-dimensional channels lined with coordinatively unsaturated Fe(II) centers. Gas adsorption isotherms at 298 K indicate that Fe(2)(dobdc) binds O(2) preferentially over N(2), with an irreversible capacity of 9.3 wt %, corresponding to the adsorption of one O(2) molecule per two iron centers. Remarkably, at 211 K, O(2) uptake is fully reversible and the capacity increases to 18.2 wt %, corresponding to the adsorption of one O(2) molecule per iron center. Mo?ssbauer and infrared spectra are consistent with partial charge transfer from iron(II) to O(2) at low temperature and complete charge transfer to form iron(III) and O(2)(2-) at room temperature. The results of Rietveld analyses of powder neutron diffraction data (4 K) confirm this interpretation, revealing O(2) bound to iron in a symmetric side-on mode with d(O-O) = 1.25(1) ? at low temperature and in a slipped side-on mode with d(O-O) = 1.6(1) ? when oxidized at room temperature. Application of ideal adsorbed solution theory in simulating breakthrough curves shows Fe(2)(dobdc) to be a promising material for the separation of O(2) from air at temperatures well above those currently employed in industrial settings.     

Two acentric mononuclear molecular complexes with unusual magnetic and ferroelectric properties

Two acentric, i.e., noncentrosymmetric, mononuclear complexes, Co(5-ATZ)(4)Cl(2), 1, and Cu(5-ATZ)(4)Cl(2), 2, where 5-ATZ is the monodentate 5-amino-1-H-tetrazole ligand, have been prepared and characterized. Both complexes crystallize in the tetragonal system with the P4nc space group, a member of the polar noncentrosymmetric 4mm class, and thus both 1 and 2 can exhibit ferroelectric and nonlinear optical properties. Magnetic studies indicate that 1 is a paramagnetic high-spin cobalt(II) complex with a rather extensive spin-orbit coupling, modeled as a zero-field splitting parameter, D, of ±91(3) cm(-1) and with very weak long-range antiferromagnetic exchange interactions. Direct current (dc) and ac magnetic studies indicate that 2 is a paramagnetic copper(II) complex that exhibits weak ferromagnetic exchange interactions below 15 K. Both 1 and 2 exhibit ferroelectric hysteresis loops at room temperature with remanent polarizations of 0.015 μC/cm(2) and coercive electric fields of 5.5 and 5.7 kV/cm, respectively.     

Energy transmission in finite coupled plates,part II: Application to an L shaped structure

The method presented in the first of these two companion papers is applied to the case of two thin plates coupled in an L shape. Numerical calculations yield values of the vibrational energies of each plate. The influences of damping, thickness and area of the plates and of the excitation type are presented and discussed. The theoretical results are compared with results from a computerized experiment, in which special attention was given to the number and position of point velocity measurements.