Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order M?ller-Plesset perturbation theory, fourth-order M?ller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values.     

Quantitative measurement of temperature by proton resonance frequency shift at low field: a general method to correct non-linear spatial and temporal phase deformations

MRI thermometry methods are usually based on the temperature dependence of the proton resonance frequency. Unfortunately, these methods are very sensitive to the phase drift induced by the instability of the scanner which prevents any temperature mapping over long periods of time. A general method based on 3D spatial modelling of the phase drift as a function of time is presented. The MRI temperature measurements were validated on gel samples with uniform and constant temperature and with a linear temperature gradient. In the case of uniform temperature conditions, correction of the phase drift proved to be essential when long periods of acquisition were required, as bias could reach values of up to 200 degrees C in its absence. The temperature uncertainty measured by MRI was 1.2 degrees C in average over 290 min. This accuracy is coherent with the requirements for food applications especially when thermocouples are useless.     

The t#-property for integral domains

Generalizing work of Gilmer and Heinzer, we define a t#-domain to be a domain R in which for any two distinct subsets and of the set of maximal t-ideals of R. We provide characterizations of these domains, and we show that polynomial rings over t#-domains are again t#-domains. Finally, we study overrings of t#-domains.     

Reflection anisotropy spectroscopy: A new probe for the solid-liquid interface

Introducing reflection anisotropy spectroscopy (RAS) as a new probe for solid-liquid interfaces, we present results for the Au(110)/electrolyte interface which serves as a model system. We demonstrate that RAS is sensitive to surface phase transitions, step morphology, and electronic surface states. Using an empirical approach, the RA spectra are reproduced and features are identified which reflect the known character of the bias voltage driven (2x1) to (1x1) phase transition. RAS is established as an experimental technique to probe the electronic structure of solid-liquid interfaces in real time to study a wide range of interface properties.     

Magnetic response of microbially synthesized transition metal- and lanthanide-substituted nano-sized magnetites

The magnetic susceptibility (κ_RT) and saturation magnetization (M_S) of microbially synthesized magnetites were systematically examined. Transition metal (Cr, Mn, Co, Ni and Zn)- and lanthanide (Nd, Gd, Tb, Ho and Er)-substituted magnetites were microbially synthesized by the incubation of transition metal (TM)- and lanthanide (L)-mixed magnetite precursors with either thermophilic (TOR-39) or psychrotolerant (PV-4) metal-reducing bacteria (MRB). Zinc incorporated congruently into both the precursor and substituted magnetite, while Ni and Er predominantly did not. Microbially synthesized Mn- and Zn-substituted magnetites had higher κ_RT than pure biomagnetite depending on bacterial species and they exhibited a maximum κ_RT at 0.2 cationic mole fraction (CMF). Other TMs’ substitution linearly decreased the κ_RT with increasing substitution amount. Based on the M_S values of TM- and L-substituted magnetite at 0.1 and 0.02 CMF, respectively, Zn (90.7 emu/g for TOR-39 and 93.2 emu/g for PV-4)- and Mn (88.3 emu/g by PV-4)-substituted magnetite exhibited higher M_S than standard chemical magnetite (84.7 emu/g) or pure biomagnetite without metal substitution (76.6 emu/g for TOR-39 and 80.3 emu/g for PV-4). Lanthanides tended to decrease M_S, with Gd- and Ho-substituted magnetites having the highest magnetization. The higher magnetization of microbially synthesized TM-substituted magnetites by the psychrotroph, PV-4 may be explained by the magnetite formation taking place at low temperatures slowing mechanics, which may alter the magnetic properties compared to the thermophile, through suppression of the random distribution of substituted cations.     

Epitaxial LSMO films grown on MgO single crystalline substrates

The manganite La_0.67Sr_0.33MnO₃ (LSMO) layers are deposited on single crystal MgO(0 0 1) substrates using a magnetron dc sputtering. The crystalline perfection of the layers, both the as-prepared and the annealed, are characterized by X-ray diffraction technique, rocking curve measurements, Rutherford backscattering spectroscopy (RBS) and transmission electron microscopy (TEM). TEM analyses give evidence of the epitaxial growth of the annealed LSMO with a nanocrystalline surface layer. The temperature dependence of resistance in the 77-340 K range is measured by a standard four-probe technique. While the as-prepared film does not show any transition from paramagnetic to ferromagnetic state, the film annealed in oxygen shows steep R(T) dependence with a peak at 330 K and maximal slope (dR/dT) at 290 K where the maximal sensitivity is 3% K⁻¹.     

Time- and space-resolved spectroscopy of dynamic hohlraum interiors

A dynamic hohlraum is created when an annular z-pinch plasma implodes onto a cylindrical 0.014 g/cc 6-mm-diameter CH₂ foam. The impact launches a radiating shock that propagates toward the axis at 350 μm/ns. The radiation trapped by the tungsten z-pinch plasma forms a 200 eV hohlraum that provides X-rays for indirect drive inertial confinement fusion capsule implosion experiments. We are developing the ability to diagnose the hohlraum interior using emission and absorption spectroscopy of Si atoms added as a tracer to the central portion of the foam. Time- and space-resolved Si spectra are recorded with an elliptical crystal spectrometer viewing the cylindrical hohlraum end-on. A rectangular aperture at the end of the hohlraum restricts the field of view so that the 1D spectrometer resolution corresponds approximately to the hohlraum radial direction. This enables distinguishing between spectra from the unshocked radiation-heated foam and from the shocked foam. Typical spectral lines observed include the Si Lyα with its He-like satellites and the He-like resonance sequence including Heα, Heβ, and Heγ, along with some of their associated Li-like satellites. Work is in progress to infer the hohlraum conditions using collisional–radiative modeling that accounts for the radiation environment and includes both opacity effects and detailed Stark broadening calculations. These 6-mm-scale radiation-heated plasmas might eventually also prove suitable for testing Stark broadening line profile calculations or for opacity measurements.     

Vector-valued perturbed equilibrium problems

The goal of this paper is to prove some general vector-valued perturbed equilibrium principles and some existence results of vector equilibrium points for bifunctions satisfying a new natural notion of lower semi-continuity. We obtain these results by going through a new concept of approximative equilibrium point.     

Determination of trace amounts of cobalt in water by solid-phase spectrophotometry after preconcentration on a nitroso R salt chelating resin

A sensitive method for the determination of microamounts of cobalt by ion-exchanger spectrophotometry has been developed. The chromogenic agent, Nitroso-R-Salt (NRS), was loaded on an anionic-exchange resin (Amberlite CG-400). The absorbance of the NRS-cobalt complex on the chelating resin was measured at 508 nm. The best conditions for the preconcentration of cobalt on the resin before the spectrophotometric determination were a pH value of 6, temperature of 80 °C, and heating times of 45 or 90 min for 50 and 400 ml of sample, respectively. The detection limits were 27 ng/ml (50-ml samples) and 1.8 ng/ml (400-ml samples). Interference by other metals was investigated. The method is useful for determination of cobalt in natural waters.