Pd-mediated activation of molecular oxygen: Pd(0) versus direct insertion

In developing environmentally benign chemistries, it is most important to use dioxygen directly in lieu of toxic and/or corrosive stoichiometric oxidants. Unfortunately, for many processes such direct oxidations have not yet become practical. To help develop such processes, we elucidate here the mechanism for the reaction of molecular oxygen with toluene-solvated palladium-hydride complex using quantum mechanics (B3LYP/LACVP** with the PBF polarizable continuum solvent model) for Pd(II-)((-)sparteine)(H)(Cl) in the presence of base, specifically focusing on the pathways proceeding through Pd(0). The lowest barrier Pd(0) pathway proceeds through a rate-determining base-assisted deprotonation of the palladium, followed by the association of molecular oxygen and the subsequent loss of chloride, forming the corresponding eta(2)-peroxo-palladium complex. We also examine the spin transition and the completion of the reaction to form PdCl(2) and H2O2. Together with our previously published Pd-H/O2 direct insertion mechanism, these reports provide a complete mapping of the possible pathways for reoxidation of palladium hydride with molecular oxygen. For this particular system, we conclude that direct insertion is preferred (DeltaDeltaH++ = 6.2 kcal/mol, DeltaDeltaG++ = 7.5 kcal/mol) and trace this preference to the bidentate character of sparteine and the lack of pi-accepting ligands. Suggestions are included for how this preference can be switched.     

Parallel implementation of a direct method for calculating electrostatic potentials

The authors present a method for calculating the electrostatic potential directly in a straightforward manner. While traditional methods for calculating the electrostatic potential usually involve solving the Poisson equation iteratively, the authors obtain the electrostatic interaction potential by performing direct numerical integration of the Coulomb-law expression using finite-element functions defined on a grid. The singularity of the Coulomb operator is circumvented by an integral transformation and the resulting auxiliary integral is obtained using Gaussian quadrature. The three-dimensional finite-element basis is constructed as a tensor (outer) product of one-dimensional functions, yielding a partial factorization of the expressions. The resulting algorithm has, without using any prescreening or other computational tricks, a formal computational scaling of Omicron(N4/3), where N is the size of the grid. The authors show here how to implement the method for efficiently running on parallel computers. The matrix multiplications of the innermost loops are completely independent, yielding a parallel algorithm with the computational costs scaling practically linearly with the number of processors.     

The (1 X 1) --> hexagonal structural transition on Pt(100) studied by high-energy resolution core level photoemission

The (1 X 1) --> quasihexagonal (HEX) phase transition on a clean Pt(100) surface was investigated by monitoring the time evolution of the Pt4f(72) core level photoemission spectra. The spectral component originating from the atoms forming the (1x1) metastable unreconstructed surface was found at -570+/-20 meV with respect to the bulk peak. Ab initio calculations based on density functional theory confirmed the experimental assignment. At temperatures above 370 K, the (1 X 1) phase irreversibly reverts to the more stable HEX phase, characterized by a surface core level shifted component at -185 +/ -40 meV. By analyzing the intensity evolution of the core level components, measured at different temperatures in the range of 393 - 475 K, we determined the activation energy of the phase transformation, E = 0.76 +/- 0.04 eV. This value is considerably lower than the one previously determined by means of low energy electron diffraction. Possible reasons for this discrepancy are discussed.     

Oxygen adsorption on Mo(112) surface studied by ab initio genetic algorithm and experiment

Density functional theory in combination with genetic algorithm is applied to determine the atomic models of p(1x2) and p(1x3) surface structures observed upon oxygen adsorption on a Mo(112) surface. The authors' simulations reveal an unusual flexibility of Mo(112) resulting in oxygen-induced reconstructions and lead to more stable structures than any suggested so far. Comparison of the stabilities of the predicted models shows that different p(1x2) and p(1x3) structures may coexist over a wide range of oxygen pressures. A pure p(1x2) structure can be obtained only in a narrow region of oxygen pressures. In contrast, a pure p(1x3) structure cannot exist as a stable phase. The results of simulations are fully supported by a multitude of experimental data obtained from low energy electron diffraction, x-ray photoelectron spectroscopy, and scanning tunneling microscopy.     

Buffer capacity of humic acid: thermodynamic approach

Commercial humic acid was dialyzed and characterized by infrared, UV/vis spectroscopy, (13)C NMR spectrometry, thermogravimetry, and elemental analysis. The dialyzed humic acid was titrated with HNO(3) and NaOH in order to obtain the buffer capacity value (beta). The humic acid presented buffer behavior by base and acid addition, and moreover, an excellent buffer capacity by addition of NaOH. Humic acid showed buffer action between pH 5.5 and 8.0, and a maximum buffer capacity at pH 6.0. The same study was followed calorimetrically to determinate the enthalpy of interaction between H(+)/OH(-) and buffer, which resulted in a maximum enthalpy of -38.49 kJ mol(-1) at pH 6.0. This value suggests that the buffer activity is based on chemisorption of proton and hydroxyl.     

Automated preparation method for colloidal crystal arrays of monodisperse and binary colloid mixtures by contact printing with a pintool plotter

Photonic crystals and photonic band gap materials with periodic variation of the dielectric constant in the submicrometer range exhibit unique optical properties such as opalescence, optical stop bands, and photonic band gaps. As such, they represent attractive materials for the active elements in sensor arrays. Colloidal crystals, which are 3D gratings leading to Bragg diffraction, are one potential precursor of such optical materials. They have gained particular interest in many technological areas as a result of their specific properties and ease of fabrication. Although basic techniques for the preparation of regular patterns of colloidal crystals on structured substrates by self-assembly of mesoscopic particles are known, the efficient fabrication of colloidal crystal arrays by simple contact printing has not yet been reported. In this article, we present a spotting technique used to produce a microarray comprising up to 9600 single addressable sensor fields of colloidal crystal structures with dimensions down to 100 mum on a microfabricated substrate in different formats. Both monodisperse colloidal crystals and binary colloidal crystal systems were prepared by contact printing of polystyrene particles in aqueous suspension. The array morphology was characterized by optical light microscopy and scanning electron microscopy, which revealed regularly ordered crystalline structures for both systems. In the case of binary crystals, the influence of the concentration ratio of the large and small particles in the printing suspension on the obtained crystal structure was investigated. The optical properties of the colloidal crystal arrays were characterized by reflection spectroscopy. To examine the stop bands of the colloidal crystal arrays in a high-throughput fashion, an optical setup based on a CCD camera was realized that allowed the simultaneous readout of all of the reflection spectra of several thousand sensor fields per array in parallel. In agreement with Bragg's relation, the investigated arrays exhibited strong opalescence and stop bands in the expected wavelength range, confirming the successful formation of highly ordered colloidal crystals. Furthermore, a narrow distribution of wavelength-dependent stop bands across the sensor array was achieved, demonstrating the capability of producing highly reproducible crystal spots by the contact printing method with a pintool plotter.     

Spatially resolved product formation in the reaction of formic acid with calcium carbonate (1014): the role of step density and adsorbed water-assisted ion mobility

The reaction of calcium carbonate (1014) single-crystal surfaces with formic acid (HCOOH) vapor was investigated using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). AFM images indicate the reaction produces rather well-defined crystallites, preferentially at step edges and at distinct angles to one another and mirroring the rhombohedral structure of the calcite surface, while exposing unreacted carbonate surface. The size and surface density of the crystallites depend upon substrate step density, exposure time, and relative humidity. XPS data confirmed the crystallite composition as the expected calcium formate product. The AFM images show erosion and pit formation of the calcite surface in the vicinity of the product crystallites, clearly providing the spatially resolved characterization of the source of Ca ions. AFM experiments exploring the effects of water vapor on the reacted surface show that the calcium formate crystallites are mobile under conditions of high relative humidity, combining to form larger crystallites and nanometer-sized crystals with an orthorhombohedral habit consistent with the alpha form, as confirmed by X-ray diffraction. The implications for the reactions described here are discussed.     

On locally definitizable matrix functions

We study analytic properties of special classes of matrix functions (locally definitizable and locally Nevanlinna functions) by methods of operator theory. The aim of this paper is to prove that if G(λ) is a locally definitizable or locally generalized matrix Nevanlinna function, then ?(G(λ))^?1 belongs to the same class.     

Inverse scattering for the homogeneous dispersive anisotropic slab using transient electromagnetic fields

An inverse scattering problem for a slab containing a homogeneous dispersive anisotropic medium is investigated. The inverse problem is to recover two three-dimensional dyadic susceptibility kernels from knowledge of the scattering kernels. Time domain techniques involving transient electromagnetic plane waves, wave splitting, invariant imbedding and a Green function technique are used. The inverse problem is separated into two parts: The Dynamics Inverse Problem (DIP) and Retrieval of Interior Parameters (RIP). Furthermore, mirror images and the Mirror Image Pair (MIP) are discussed. The DIP is solved numerically by using an inverse algorithm and scattering data from one MIP. The RIP turns out to be well posed (system of Volterra equations of the second kind) and needs in general two MIPs. In the DIP, the equations for initial values using transmission data have in general not a unique solution. Constraints and simplifications for certain classes of media are pointed out. Numerical examples, including noisy data, illustrate the analysis.     

The Guinness Molecules for the Carbohydrate Formula

A systematic review and analysis of the most stable spatial arrangements of n carbon, n oxygen, and 2n hydrogen atoms including vibrational zero‐point energy up to n = 5 shows that small‐molecule aggregates win, typically followed by thermally unstable molecules, before kinetically stable molecules and finally carbohydrates are found. Near n ≈ 60 a crossover to carbon allotropes and ice as the global minimum structure is expected and the asymptotic limit is most likely graphite and ice. Implications for astrochemical and fermentation processes are discussed. Density functionals like B3LYPD3 are found to describe these energy sequences quite poorly, mostly due to an overestimated stability of carbon in high oxidation states.