Rotational state populations and angular distributions on surface scattered molecules: No on graphite

Rotational state populations and angular distributions of NO molecules were determined after the scattering of a supersonic beam from a graphite surface at different surface temperatures. The angular distributions exhibit an isotropic and a specular part. The rotational population of the scattered molecules can be described by Boltzmann distributions with identical temperatures for both electronic ground states²Π_½ and²Π_3/2 and both scattering components. The rotational temperature agrees with the surface temperature below 170 K and converges to a constant value of 250 K for surface temperatures higher than 350 K.     

The determination of silica by conway's microdiffusion technique

A new approach is suggested to the determination of silica. Silica is converted to volatile silicon-fluoride compounds by the action of hydrofluoric acid and is quatitatively isolated by Conway's microdiffusion technique in a polypropylene cell. To promote diffusion, a sulphuric acid medium is used; ethylene glycol serves as absorbent. Quantities of 20-70 μ SiO₂ per 0.5 ml were tested, with quantitative recovery. The silica was determined spectrophotometrically by the molybdenum blue method.     

Reduction of CuO and Cu2O with H2: H embedding and kinetic effects in the formation of suboxides

Time-resolved X-ray diffraction, X-ray absorption fine structure, and first-principles density functional calculations were used to investigate the reaction of CuO and Cu(2)O with H(2) in detail. The mechanism for the reduction of CuO is complex, involving an induction period and the embedding of H into the bulk of the oxide. The in-situ experiments show that, under a normal supply of hydrogen, CuO reduces directly to metallic Cu without formation of an intermediate or suboxide (i.e., no Cu(4)O(3) or Cu(2)O). The reduction of CuO is easier than the reduction of Cu(2)O. The apparent activation energy for the reduction of CuO is about 14.5 kcal/mol, while the value is 27.4 kcal/mol for Cu(2)O. During the reduction of CuO, the system can reach metastable states (MS) and react with hydrogen instead of forming Cu(2)O. To see the formation of Cu(2)O, one has to limit the flow of hydrogen, slowing the rate of reduction to allow a MS --> Cu(2)O transformation. These results show the importance of kinetic effects for the formation of well-defined suboxides during a reduction process and the activation of oxide catalysts.     

Experimental and theoretical studies on the reaction of H(2) with NiO: role of O vacancies and mechanism for oxide reduction.

Reduction of an oxide in hydrogen is a method frequently employed in the preparation of active catalysts and electronic devices. Synchrotron-based time-resolved X-ray diffraction (XRD), X-ray absorption fine structure (NEXAFS/EXAFS), photoemission, and first-principles density-functional (DF) slab calculations were used to study the reaction of H(2) with nickel oxide. In experiments with a NiO(100) crystal and NiO powders, oxide reduction is observed at atmospheric pressures and elevated temperatures (250-350 degrees C), but only after an induction period. The results of in situ time-resolved XRD and NEXAFS/EXAFS show a direct NiO-->Ni transformation without accumulation of any intermediate phase. During the induction period, surface defect sites are created that provide a high efficiency for the dissociation of H(2). A perfect NiO(100) surface, the most common face of nickel oxide, exhibits a negligible reactivity toward H(2). The presence of O vacancies leads to an increase in the adsorption energy of H(2) and substantially lowers the energy barrier associated with the cleavage of the H-H bond. At the same time, adsorbed hydrogen can induce the migration of O vacancies from the bulk to the surface of the oxide. A correlation is observed between the concentration of vacancies in the NiO lattice and the rate of oxide reduction. These results illustrate the complex role played by O vacancies in the mechanism for reduction of an oxide. The kinetic models frequently used to explain the existence of an induction time during the reduction process can be important, but a more relevant aspect is the initial production of active sites for the rapid dissociation of H(2).     

Quantum chemical study of nickel(II) complexes with cyclic diimine ligands on the base of bis[3,3′-iminopropyl]methylamine

A quantum chemical study of spatial and electronic structures of molecules in the frame complexes, bis[3,3′(RR′)-ketiminepropyl]methylamine nickel dichlorides, where R = H, CH₃, and R′ = H, CH₃, has been performed by DFT(B3LYP/LANL2DZ) method. The molecules of these complexes were found to be in a triplet state. Energy stability of the endo form of the complex molecules was shown. In the molecule of bis[3,3′-aldiminopropyl]methylamine nickel dichloride (R = R′ = H), a considerable strengthening of the bond Ni-N(amine) takes place when passing from the diamagnetic into paramagnetic state, and all bonds Ni-N become equivalent with respect to interatomic distance values. The topology analysis of the electron density for the complexes with R = R′ =H and R = R′ = CH₃ was carried out. It is stated that all Ni-N bonds are covalent in the molecules of paramagnetic complexes.     

Numerical prediction of absolute crystallization rates in hard-sphere colloids

Special computational techniques are required to compute absolute crystal nucleation rates of colloidal suspensions. Using crystal nucleation of hard-sphere colloids as an example, we describe in some detail the novel computational tools that are needed to perform such calculations. In particular, we focus on the definition of appropriate order parameters that distinguish liquid from crystal, and on techniques to compute the kinetic prefactor that enters in the expression for the nucleation rate. In addition, we discuss the relation between simulation results and theoretical predictions based on classical nucleation theory.     

Interpolymer complex formation of some nonionogenic polymers with linear and crosslinked polyacrylic acid

The formation of interpolymer complexes on the surface of crosslinked poly (acrylic acid) with some nonionogenic polymers is compared with the complex formation in analogous linear polymer systems. The behavior of these systems is compared with that of complexes of two oppositely charged polyelectrolytes. The concentration redistribution of the linear polymer in the system polyelectrolyte network-polymer solution and the degree of swelling of this network in these solutions were determined. © 1994 John Wiley & Sons, Inc.     

Mod 2 indecomposable orthogonal invariants

Over an algebraically closed base field k of characteristic 2, the ring R^G of invariants is studied, G being the orthogonal group O(n) or the special orthogonal group SO(n) and acting naturally on the coordinate ring R of the m-fold direct sum kⁿ⊕?⊕kⁿ of the standard vector representation. It is proved for O(n) (n?2) and for SO(n) (n?3) that there exist m-linear invariants with m arbitrarily large that are indecomposable (i.e., not expressible as polynomials in invariants of lower degree). In fact, they are explicitly constructed for all possible values of m. Indecomposability of corresponding invariants over immediately follows. The constructions rely on analysing the Pfaffian of the skew-symmetric matrix whose entries above the diagonal are the scalar products of the vector variables.     

Leading non-cancelling infrared divergences in perturbative QCD

In perturbative QCD, for the inclusive cross section for the scattering of two coloured particles, we identify graphs which contribute to the general leading order α_s(α_s lnλ)ⁿ of uncancelled IR divergences, and we sum these contributions (λ is the IR cut-off). The work is done in the Coulomb gauge; an appendix discusses the Feynman gauge.