The chemistry and physics of molecular surfaces

Configuration interaction calculations are carried out to study the potential energy surface for the system Ar-Ar ₂ ⁺ . An all-electron as well as a pseudopotential treatment is employed. It is found that in the perpendicular Ar approach the Ar ₂ ⁺ partner remains essentially unchanged and the potential can be characterized by an electrostatic ion-induced dipole interaction. In the collinear mode of Ar approach the Ar ₂ ⁺ bond separation increases considerably, the charge is redistributed and the interaction can be characterized as chemical bonding. The minimum on the surface is found to be the linear symmetric molecule with bond lengths of 2.62 Å. The optimum structure in the perpendicular approach lies 0.13 eV above the minimum and is the T-shaped molecule in which the Ar is 3.65 Å away from the midpoint of the Ar ₂ ⁺ (r=2.46 Å) system; the best equilateral triangle structure has a bond length of 2.99 Å but is found to lie 0.64 eV above the Ar ₃ ⁺ minimum. The dissociation energy into Ar ₂ ⁺ + Ar is calculated to be 0.16 eV in reasonable agreement with experimental values of 0.21 eV. The potential curves for the four lowest states of Ar ₂ ⁺ are also treated.     

Recent developments in zinc oxide target chemistry

Zinc oxide targets irradiated with high energy protons at the Los Alamos Meson Physics Facility (LAMPF) contain a number of radioactive spallation products in quantities large enough to warrant recovery. This paper describes methods for recovering⁷Be,⁴⁶Sc, and⁴⁸V from such targets and offers suggestions on possible ways to recover additional isotopes. The proposed methods are based on traditional precipitation and ion exchange techniques, are readily adaptable to hot cell use, and produce no hazardous waste components. The products are obtained in moderate to high yields and have excellent radionuclidic purity.     

Wettability of zinc oxide surfaces with controllable structures

Zinc oxide (ZnO) surfaces with controllable structures (i.e, microstructure, nanostructure, and micronanobinary structure) have been created by controlling pH at < 4 or > 10.5 in the Zn(gray) + H2O2 reaction. The resulting surface shows superhydrophobicity. It is found that the water contact angle (CA) of the surface with micronanobinary structure is greater than that of nanostructure and that of nanostructure is greater than that of the microstructure. Theoretical analysis is completely in agreement with the experimental results.     

Directed crystallisation of zinc oxide on patterned surfaces

Patterned self-assembled monolayers of functionalised alkane thiols were prepared on gold substrates, using UV-photolithography. Two alkane thiols, 11-mercaptoundecanoic acid (MUA) and a fluorinated decane thiol (FDT, CF3(CF2)7CH2CH2SH) were used to fabricate chemically structured surfaces which served as templates for zinc oxide (ZnO) crystallisation. When these patterns, containing high (MUA) and low (FDT) surface energy regions were exposed to a 10 mM zinc nitrate crystallising solution, nucleation occurred selectively on the low energy regions. After 90 min, hexagonal prisms had grown upright on these areas. The crystal growth is uniform with a crystal length of about 1 mum and a diameter between 50 and 100 nm. We attribute the selective growth to a combination of crystallographic frustration of the zinc ions on the high energy regions and an accumulation of hydroxide ions on the low energy regions.     

The physics and chemistry of solar cells

The physics of the photovoltaic effect is analyzed using the example of a frontwall solar cell. The effect results from the interplay of the emitter, in which minority cariers are generated via absorbed light an diffuse to the junction, and the junction, in which the essential voltage drop occurs. The interplay is established by the minority carrier density at the emitter-junction interface, acting as prominent boundary condition, and connecting current through the device with applied voltage.The chemistry of the interlayer between emitter and junction has essential influence on this boundary condition by determining interface recombination and space charge. Both of these determine band connection and performance of the device.A brief review of material properties in the light of the basic cell operation is given.     

An SKP and EIS investigation of amine adsorption on zinc oxide surfaces

A metal/oxide/polymer ‘interphase’ with mixed organic–inorganic nature insures the high stability and the strength of the adhesive joints in a variety of corrosive environments. To model the interaction of epoxy resin with a metal surface, the interaction of amines of different structure with oxidized zinc surfaces was studied by Scanning Kelvin Probe (SKP), FTIR microscopy in atmospheric conditions, and a.c. and d.c. electrochemical techniques in the aqueous electrolyte. It was shown that bidentate ligand‐ethylendiamine, forming stable chelate complexes reacts with zinc oxide with redeposition of the interphase. In air and water electrolyte, this ligand shifts the potential of Zn/ZnO electrode to the level of the oxide‐free zinc. The amines with low chelating property show low effect on the potential of Zn/ZnO. The SKP was used to measure the potential drop at epoxy resin/zinc interface. On this basis, SKP is proposed as a sensitive nondestructive technique to characterize in situ the interaction of the resin with the metal and the subsequent formation of the interphase in the metal–polymer joints. Copyright © 2010 John Wiley & Sons, Ltd.     

Superhydrophobic surfaces using selected zinc oxide microrod growth on ink-jetted patterns

The synthesis and properties of superhydrophobic surfaces based on binary surface topography made of zinc oxide (ZnO) microrod-decorated micropatterns are reported. ZnO is intrinsically hydrophilic but can be utilized to create hydrophobic surfaces by creating artificial roughness via microstructuring. Micron scale patterns consisting of nanocrystalline ZnO seed particles were applied to glass substrates with a modified ink-jet printer. Microrods were then grown on the patterns by a hydrothermal process without any further chemical modification. Water contact angle (WCA)(1) up to 153° was achieved. Different micro array patterned surfaces with varying response of static contact angle or sessile droplet analysis are reported.     

Scalar nonlinearities in physics and chemistry

Scalar nonlinearities are operators of the form N(u) = 〈Au, u〉Bu, where A, B are linear operators, and 〈·,·〉 is the inner product in a Hilbert space ??. This paper reviews applications of scalar nonlinearities. We show that operators of the form N(u) are found in equations that describe phenomena of classical mechanics, open systems of quantum mechanics, and chemical physics.     

Interaction between poly(styrene-acrylic acid) latex nanoparticles and zinc oxide surfaces

Latex particles with an average diameter of 70 nm, functionalized at the surface with carboxylic groups, are chemically coated by layer-by-layer deposition onto a spherical probe attached on an atomic force microscope cantilever. The forces between poly(styrene-acrylic acid) latex nanoparticles and differently terminated zinc oxide surfaces are studied by a homemade atomic force microscope based apparatus. The results confirmed a preferred adhesion of the latex particles to zinc-terminated ZnO faces, 0001, compared to oxygen-terminated and apolar faces. The method proposed allows the measurement of the interaction between nanometric particles and planar surfaces, which may be of interest for different applications in surface and colloid sciences.     

Adsorption of poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) polymers on zinc, zinc oxide, iron, and iron oxide surfaces

The adsorption of poly(vinyl formamide) (PVFA) and the statistic copolymers poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) onto zinc and iron metal particles as well as their oxides was investigated. The adsorbates were characterized by means of XPS, DRIFT spectroscopy, wet chemical analysis, and solvatochromic probes. Dicyano-bis-(1,10-phenanthroline)-iron(II) (1), 3-(4-amino-3-methylphenyl)-7-phenyl-benzo-[1,2-b:4,5-b']difuran-2,6-dione (2), and 4-tert-butyl-2-(dicyano-methylene)-5-[4-(diethylamino)-benzylidene]-Δ(3)-thiazoline (3) as solvatochromic probes were coadsorbed onto zinc oxide to measure various effects of surface polarity. The experimental findings showed that the adsorption mechanism of PVFA and PVFA-co-PVAm strongly depends on the degree of hydrolysis of PVFA and pH values and also on the kind of metal or metal oxide surfaces that were employed as adsorbents. The adsorption mechanism of PVFA/PVFA-co-PVAm onto zinc oxide and iron oxide surfaces is mainly affected by electrostatic interactions. Particularly in the region of pH 5, the adsorption of PVFA/PVFA-co-PVAm onto zinc and iron metal particles is additionally influenced by redox processes, dissolution, and complexation reactions.     

The synthesis of zinc oxide nanostructures

It was proposed to synthesize quasi-one-dimensional nano-sized zinc oxide crystals by the vapor-liquid-crystal mechanism during the gas phase epitaxy. An array of nanowhiskers randomly distributed throughout the polished surface of silicon wafer was grown. The structure and properties of whiskers were determined.     

Chemical physics of dispersed material surfaces

Adsorption and chemisorption processes involving hydroxy groups and coordinated water molecules on the surface of silica are discussed on the basis of information derived from infrared spectra, ESCA and thermogravimetric data. The formation of strongly adsorbed surface complexes is described in terms of changes in coordination number of silicon atoms and the concomitant lowering of surface tension.     

Highlights in chemistry and physics of polymer stabilization

Deactivation of free radicals, hydroperoxides and harmful solar radiation are the principal mechanisms increasing stability of commodity and engineering polymers. The stabilization process is accompanied by transformations of individual additives. New compounds influence specifically the integral protecting mechanism. Products contributing to the stability are most beneficial. Mechanistic data are used for optimisation of the inherent chemical efficiency and physical persistence and for explanation of deactivation of stabilizers.     

Applications of caterpillar trees in chemistry and physics

The relations of caterpillar trees (which are also known as Gutman trees and benzenoid trees) to other mathematical objects such as polyhex graphs, Clar graphs, king polyominos, rook boards and Young diagrams are discussed. Potential uses of such trees in data reduction, computational graph theory, and in the ordering of graphs are considered. Combinatorial and physical properties of benzenoid hydrocarbons can be studied via related caterpillars. It thus becomes possible to study the properties of large graphs such as benzenoid (i.e. polyhex) graphs in terms of much smaller tree graphs. Generation of the cyclic structures of wreath and generalized wreath product groups through the use of caterpillar trees is illustrated.