Ad-atom interactions with III-V semiconductor surfaces

Photoemission techniques (core level, valence band and partial yield spectroscopies) using synchrotron radiation as the excitation source have been applied to study the changes in the surface electronic structure of the (110) cleavage face of III-V semiconductor surfaces as a function of different ad-atom coverages. In this paper we concentrate on Au overlayers on GaSb and in particular address the problem of the mechanism for Fermi level pinning and the formation of Schottky barrier heights. It appears that the Fermi level pinning is fully established at a small fraction of a monolayer coverage. Core level spectroscopy gives evidence for a strong metal-semiconductor interaction leading to decomposition of GaSb at the interface. The experimental results form the basis for proposing a new model for the Schottky barrier based on defect states at the interface.     

Oxygen adsorption and the surface electronic structure of GaAs (110)

The surface electronic structure of cleaved GaAs (110) is found to be very sensitive to small amounts of adsorbed oxygen. For example, adsorbing oxygen on only a few percent of the surface Ga or As atomic sites can produce changes of a factor of two in the surface electronic structure. Thus, long range effects must be involved, and these are associated with rearrangement of the surface atoms.     

Phenoxyl radicals: H-bonded and coordinated to Cu(II) and Zn(II)

Two pro-ligands ((R)LH) comprised of an o,p-di-tert-butyl-substituted phenol covalently bonded to a benzimidazole ((Bz)LH) or a 4,5-di-p-methoxyphenyl substituted imidazole ((PhOMe)LH), have been structurally characterised. Each possesses an intramolecular O-H[dot dot dot]N hydrogen bond between the phenolic O-H group and an imidazole nitrogen atom and (1)H NMR studies show that this bond is retained in solution. Each (R)LH undergoes an electrochemically reversible, one-electron, oxidation to form the [(R)LH] (+) radical cation that is considered to be stabilised by an intramolecular O...H-N hydrogen bond. The (R)LH pro-ligands react with M(BF(4))(2).H(2)O (M = Cu or Zn) in the presence of Et(3)N to form the corresponding [M((R)L)(2)] compound. [Cu((Bz)L)(2)] (), [Cu((PhOMe)L)(2)] (), [Zn((Bz)L)(2)] and [Zn((PhOMe)L)(2)] have been isolated and the structures of .4MeCN, .2MeOH, .2MeCN and .2MeCN determined by X-ray crystallography. In each compound the metal possesses an N(2)O(2)-coordination sphere: in .4MeCN and .2MeOH the {CuN(2)O(2)} centre has a distorted square planar geometry; in .2MeCN and .2MeCN the {ZnN(2)O(2)} centre has a distorted tetrahedral geometry. The X-band EPR spectra of both and , in CH(2)Cl(2)-DMF (9 : 1) solution at 77 K, are consistent with the presence of a Cu(ii) complex having the structure identified by X-ray crystallography. Electrochemical studies have shown that each undergo two, one-electron, oxidations; the potentials of these processes and the UV/vis and EPR properties of the products indicate that each oxidation is ligand-based. The first oxidation produces [M(II)((R)L)((R)L )](+), comprising a M(ii) centre bound to a phenoxide ((R)L) and a phenoxyl radical ((R)L ) ligand; these cations have been generated electrochemically and, for R = PhOMe, chemically by oxidation with Ag[BF(4)]. The second oxidation produces [M(II)((R)L )(2)](2+). The information obtained from these investigations shows that a suitable pro-ligand design allows a relatively inert phenoxyl radical to be generated, stabilised by either a hydrogen bond, as in [(R)LH] (+) (R = Bz or PhOMe), or by coordination to a metal, as in [M(II)((R)L)((R)L )](+) (M = Cu or Zn; R = Bz or PhOMe). Coordination to a metal is more effective than hydrogen bonding in stabilising a phenoxyl radical and Cu(ii) is slightly more effective than Zn(II) in this respect.     

SuperQuat 5,5-dimethyl-4-iso-propyloxazolidin-2-one as a mimic of Evans 4-tert-butyloxazolidin-2-one

The incorporation of a gem-dimethyl group at the 5-position of a chiral oxazolidinone biases the conformation of the adjacent C(4)-stereodirecting group such that the gem-dimethyl-4-iso-propyl combination mimics a C(4)-tert-butyl group, providing higher levels of stereocontrol than a simple 4-iso-propyloxazolidinone. The generality of this principle is demonstrated with applications in stereoselective enolate alkylations, kinetic resolutions, Diels-Alder cycloadditions and Pd-catalysed asymmetric acetalisation reactions.     

Lithium amide conjugate addition for the asymmetric synthesis of 3-aminopyrrolidines

Conjugate addition of homochiral lithium amides to methyl 4-(N-benzyl-N-allylamino)but-2-enoate, chemoselective N-deprotection and concomitant cyclisation, followed by enolate functionalisation and deprotection allows access to syn- and anti-3,4-disubstituted aminopyrrolidines in > 98% d.e. and > 98% e.e.     

Persistence of microstructural evolution in irradiated metals and its consequences at high radiation exposure

Abstract

A review is presented of a very general aspect of the response of all metals subjected to displacive irradiation. This aspect is referred to as «persistence» and describes the tendency of both radiation-induced microstructural evolution and the associated changes in material properties or dimensional stability to evolve to saturation states that resist further change upon continued irradiation. It is shown that new persistent states can develop on a longer time frame associated with the late-term loss of existing microstructural components or the gain of new components, especially when transmutation and/or segregation occurs. The persistent states are often dependent on the irradiation conditions, and if these are changed, the material usually adjusts to form the persistent state characteristic of the new conditions, with the memory of the former state often lost, and sometimes leaving no visible record of the former state in the new microstructure. Depending on the microstructural components involved, the transition toward the new persistent state can occur quickly or very slowly.     

Sources of variability in distortion product otoacoustic emissions

The goal of this study was to determine the extent to which the variability seen in distortion product otoacoustic emissions (DPOAEs), among ears with normal hearing, could be accounted for. Several factors were selected for investigation, including behavioral threshold, differences in middle-ear transmission characteristics either in the forward or the reverse direction, and differences in contributions from the distortion and reflection sources. These variables were assessed after optimizing stimulus parameters for individual ears at each frequency. A multiple-linear regression was performed to identify whether the selected variables, either individually or in combination, explained significant portions of variability in DPOAE responses. Behavioral threshold at the f(2) frequency and behavioral threshold squared at that same frequency explained the largest amount of variability in DPOAE level, compared to the other variables. The combined model explained a small, but significant, amount of variance in DPOAE level at five frequencies. A large amount of residual variability remained, even at frequencies where the model accounted for significant amounts of variance.     

Using block designs in crossing number bounds

The crossing number $\mathrm{\text{CR}}\left(G\right)$ of a graph $G=\left(V,E\right)$ is the smallest number of edge crossings over all drawings of $G$ in the plane. For any $k\ge 1$, the $k$‐planar crossing number of $G,{\mathrm{\text{CR}}}_k\left(G\right)$, is defined as the minimum of $\text{CR}\left(G_1\right)+\text{CR}\left(G_2\right)+?+\text{CR}\left(G_k\right)$ over all graphs $G_1,G_2,\dots ,G_k$ with ${\cup }_{i=1}^k{G}_i=G$. Pach et al [Comput. Geom.: Theory Appl. 68 (2018), pp. 2–6] showed that for every $k\ge 1$, we have ${\text{CR}}_k\left(G\right)\le (2/k^2?1/k^3)\text{CR}\left(G\right)$ and that this bound does not remain true if we replace the constant $2/k^2?1/k^3$ by any number smaller than $1/k^2$. We improve the upper bound to $(1/k^2)\left(1+o\left(1\right)\right)$ as $k\to \infty$. For the class of bipartite graphs, we show that the best constant is exactly $1/k^2$ for every $k$. The results extend to the rectilinear variant of the $k$‐planar crossing number.