Computed Potential Energy Surfaces and Minimum Energy Pathways for Chemical Reactions

Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO_x and soot formation in hydrocarbon combustion are discussed.     

On incorporation of atomic correlation in transition-metal molecular calculations: NiH

The atomic correlation terms necessary to lead to anaccurate 4s²3d⁸-4s^t 3d⁹ separation for the Ni atom have been incorporated into all-electron MC SCF/Cl calculations for the X² Δ state of NiH. The calculated potential curve properties are significantly improved compared to calculations which dissociate to Hartree-Fock atoms.     

Membrane structure and its correlation with membrane permeability

Methods for the investigation of pore and molecular structure of synthetic membranes are reviewed. Membranes are classified as coarse-porous, fine-porous, and solution-diffusion membranes, on one hand; and homogeneous, asymmetric, and composite on the other, Pore structure of synthetic membranes can be elucidated in detail only by electron and raster electron microscopic investigations. Inspection of molecular structure requires diversely specific test probes such as low-energy neutron scattering and/or diffraction, and gas sorption and permeability measurements, as well as thermodynamic and thermomechanical analysis. Other methods used to elucidate pore and molecular structure of synthetic membranes are discussed and, concurrently, membrane structure is correlated with membrane permeability.     

On the electron affinity of Cu atom

The electron affinity (EA) of the Cu atom is computed using large STO and GTO basis sets at several levels of correlation. The best computed value is 1     

Measurement of the charging of individual dust grains in a plasma

An experiment is described for investigating the charging of dust grains in a plasma. The apparatus is a double plasma device into which single dust grains are dropped from the top. The dust charge is detected and measured by a sensitive electrometer attached to a Faraday cup on the bottom. Experiments with electrons from the emissive filaments but without plasma indicate that the grains charge to approximately the filament potential for filament bias voltages smaller in absolute value than -70 V. The charge is of order 10⁶ electrons for SiC grains 30-150 μm in diameter. At higher bias voltage the charge is reduced due to secondary emission. The charge on grains increases with grain size and is nearly independent of the filament emission current. With plasma in the device, the grains charge both positively and negatively     

Theoretical studies of the bonding of sulfur to models of the (100) surface of nickel

Electronic wavefunctions have been obtained as a function of geometry for a S atom bonded to Ni clusters consisting of 1 to 4 atoms designed to model bonding to the Ni(100) surface. Electron correlation effects were included using the generalized valence bond and configuration interaction methods. Modeling the (100) surface with four Ni atoms, we find the optimum S position to be 1.33 Å above the surface, in good agreement with the value (1.30 ± 0.10 Å) from dynamic LEED intensity calculations. The bonding is qualitatively like that in H₂S with two covalent bonds to one diagonal pair of Ni atoms. There is a S pπ pair overlapping the other diagonal pair of Ni atoms. [Deleting this pair the S moves in to a position 1.04 Å from the surface.] There are two equivalent such structures, the resonance leading to equivalent S atoms and a c(2 × 2) structure for the S overlayer. The Ni in the layer beneath the surface seems to have little effect (~0.03 Å) on the calculated geometry. Bonding the S directly above a single Ni atom leads to a much weaker bond (D_e = 3.32 eV) than does bonding in a bridge position (D_e = 5.37 eV).     

Theoretical studies of the bonding of oxygen to models of the (100) surface of nickel

Electronic wavefunctions have been obtained as a function of geometry for an O atom bonded to Ni clusters (consisting of one to five atoms) designed to model bonding to the (100) surface of Ni. Electron correlation effects were included using the generalized valence bond and configuration interaction methods. For the (100) surface, we find that the charge distribution for the full O overlay er is consistent with taking a positively charged cluster. The four surface atoms in the surface unit cell and the atom beneath the surface are important in determining the geometry, leading to a Ni⁺₅O cluster as the model for the (100) surface. The optimum oxygen position with this model is 0.96 Å above the surface (four-fold coordinate site) in good agreement with the value (0.90 ± 0.10 Å) from dynamic LEED intensity analysis. The atom beneath the surface allows important polarization effects for the positively charged cluster. The bonding to the surface involves bridging two diagonal surface Ni atoms. There is an O(2pπ) pair which overlaps the other diagonal pair of Ni atoms leading to nonbonded repulsions which increase the distance above the surface. There are two equivalent such structures, the resonance leading to a c(2 × 2) structure for the O overlayer.     

Theoretical studies of the geometries of O and S overlayers on the (100) surface of nickel

Geometries for O and S overlayers on the (100) surface of Ni have been calculated using $\text{a b initio}$ wavefunctions for O and S bonded to small clusters of Ni atoms (1 to 5 Ni atoms). The calculated distance of the adatom from the surface is 0.96 Å and 1.33 Å for O and S, respectively, in excellent agreement with the results of dynamic LEED intensity calculations, 0.9 ± 0.1 Å and 1.3 ± 0.1 Å, respectively. This indicates that accurate geometries of chemisorbed atoms may be obtained from calculations using clusters.     

Chromatographic investigations into the interaction between proteins and polymer matrices

Summary Chromatographic investigations with two enzymes and selected low-molecular-weight compounds of different pk_a on three different inert gels (matrices) commonly used for enzyme separation and immobilization showed that considerable deviations from the theoretical elution volumes occur at low ionic strength. These deviations are explained in terms of ionic and hydrophobic interaction between gel matrix and solute.