Atomic imaging of atomic layer deposition oxide nucleation with trimethylaluminum on As-rich InGaAs(001) 2 × 4 vs Ga/In-rich InGaAs(001) 4 × 2

Formation of a contaminant free, flat, electrically passive interface to a gate oxide such as a-Al(2)O(3) is the critical step in fabricating III-V metal oxide semiconductor field effect transistors; while the bulk oxide is amorphous, the interface may need to be ordered to prevent electrical defect formation. A two temperature in situ cleaning process is shown to produce a clean, flat group III or group V rich InGaAs surface. The dependence of initial surface reconstruction and dosing temperature of the seeding of aluminum with trimethylaluminum dosing is observed to produce an ordered unpinned passivation layer on InGaAs(001)-(4 × 2) surface at sample temperatures below 190 °C. Conversely, the InGaAs(001)-(2 × 4) surface is shown to generate an unpinned passivation layer with a seeding temperature up to 280 °C. For both reconstructions, the chemical drive force is consistent with formation of As-Al-As bonds. The optimal seed layer protects the surface from background contamination.     

An ultrasonic array sensor for spacecraft leak direction finding

We have developed an ultrasonic array sensor useable for locating air leaks in manned spacecraft and have found that this sensor locates leaks in a 1-m² plate to within 2 cm. The sensor consists of a 63-element multiplexed array plus a reference element, all constructed from a single PZT disc and a printed circuit board. Cross-correlations of signals from the array elements with signals from the single reference element provide a measurement of the leak noise passing through the spacecraft skin under the array. A spatial Fourier transform reveals the dominant direction of propagation. Triangulation from multiple sensor locations can be used to find the source of the leak.     

(1)H-(13)C INEPT MAS NMR correlation experiments with (1)H-(1)H mediated magnetization exchange to probe organization in lipid biomembranes

Two-dimensional (1)H-(13)C INEPT MAS NMR experiments utilizing a (1)H-(1)H magnetization exchange mixing period are presented for characterization of lipid systems. The introduction of the exchange period allows for structural information to be obtained via (1)H-(1)H dipolar couplings but with (13)C chemical shift resolution. It is shown that utilizing a RFDR recoupling sequence with short mixing times in place of the more standard NOE cross-relaxation for magnetization exchange during the mixing period allowed for the identification and separation of close (1)H-(1)H dipolar contacts versus longer-range inter-molecular (1)H-(1)H dipolar cross-relaxation. These 2D INEPT experiments were used to address both intra- and inter-molecular contacts in lipid and lipid/cholesterol mixtures.     

Binding affinity of alkynes and alkenes to low-coordinate iron

We report the synthesis, spectroscopy, and structural characterization of iron-alkyne and -alkene complexes of the type L(Me)Fe(ligand) [L(Me) = bulky beta-diketiminate, ligand = HCCPh, EtCCEt, CH2CHPh, EtCHCHEt, HCC(p-C6H4OCH3), HCC(p-C6H4CF3)]. The neutral ligand exchanges rapidly at room temperature, and the equilibrium constants have been measured or estimated. The binding affinity toward the low-coordinate Fe follows the trend HCCPh > EtCCEt > CH2CHPh > EtCHCHEt approximately PPh3 > benzene > N2. This trend is consistent with a model in which pi back-bonding from the formally Fe(I) center is the dominant interaction in determining the relative binding affinities. In nitrogenase, alkynes are reduced while alkenes are unreactive, and this work suggests that the different binding affinities to low-coordinate Fe might explain the differential activity of the enzyme toward these two substrates.     

Can the nearly conformal sextet gauge model hide the Higgs impostor?

New results are reported from large scale lattice simulations of a frequently discussed strongly interacting gauge theory with a fermion flavor doublet in the two-index symmetric (sextet) representation of the SU(3) color gauge group. We find that the chiral condensate and the mass spectrum of the sextet model are consistent with chiral symmetry breaking in the limit of vanishing fermion mass. In contrast, sextet fermion mass deformations of spectral properties are not consistent with leading conformal scaling behavior near the critical surface of a conformal theory. A recent paper could not resolve the conformal fixed point of the gauge coupling from the slowly walking scenario of a very small nearly vanishing β-function (DeGrand et al. [3]). It is argued that overall consistency with our new results is resolved if the sextet model is close to the conformal window, staying outside with a very small non-vanishing β-function. The model would exhibit then the simplest composite Higgs mechanism leaving open the possibility of a light scalar state with quantum numbers of the Higgs impostor. It would emerge as the pseudo-Goldstone dilaton state from spontaneous symmetry breaking of scale invariance. We will argue that even without association with the dilaton, the scalar Higgs-like state can be light very close to the conformal window. A new Higgs project of sextet lattice simulations is outlined to resolve these important questions.     

Electronically unsaturated three-coordinate chloride and methyl complexes of iron,cobalt, and nickel

Three-coordinate organometallic complexes are rare, especially with the prototypical methyl ligand. Using a hindered, rigid bidentate ligand (L), it is possible to create 12-electron methyliron(II) and 13-electron methylcobalt(II) complexes. These complexes are thermally stable, and (1)H NMR spectra suggest that the low coordination number is maintained in solution. Attempts to create the 14-electron LNiCH(3) led instead to the three-coordinate nickel(I) complex LNi(THF). Single crystals of LMCH(3) are isomorphous with the new three-coordinate chloride complexes LNiCl and LCoCl. Along with the recently reported LFeCl (Smith, J. M.; Lachicotte, R. J.; Holland, P. L. Chem. Commun. 2001, 1542), these are the only examples of three-coordinate iron(II), cobalt(II), and nickel(II) complexes with terminal chloride ligands, enabling the systematic evaluation of the effect of coordination number and metal identity on M-Cl bond lengths. Electronic structure calculations predict the ground states of the trigonal complexes.     

Ligand macrocycle structural effects on copper-dioxygen reactivity

With the goal of understanding how the nature of the tridentate macrocyclic supporting ligand influences the relative stability of isomeric mu-eta 2:eta 2-peroxo- and bis(mu-oxo)dicopper complexes, a comparative study was undertaken of the O2 reactivity of Cu(I) compounds supported by the 10- and 12-membered macrocycles, 1,4,7-R3-1,4,7-triazacyclodecane (R3TACD; R = Me, Bn, iPr) and 1,5,9-triisopropyl-1,5,9-triazacyclododecane (iPr3TACDD). While the 3-coordinate complex [(iPr3TACDD)Cu]SbF6 was unreactive with O2, oxygenation of [(R3TACD)Cu(CH3CN)]X (R = Me or Bn; X = ClO4- or SbF6-) at -80 degrees C yielded bis(mu-oxo) species [(R3TACD)2Cu2(mu O)2]X2 as revealed by UV-vis and resonance Raman spectroscopy. Interestingly, unlike the previously reported system supported by 1,4,7-triisopropyl-1,4,7-triazacyclononane (iPr3TACN), which yielded interconverting mixtures of peroxo and bis(mu-oxo) compounds (Cahoy, J.; Holland, P. L.; Tolman, W. B. Inorg. Chem. 1999, 38, 2161), low-temperature oxygenation of [(iPr3TACD)Cu(CH3CN)]SbF6 in a variety of solvents cleanly yielded a mu-eta 2:eta 2-peroxo product, with no trace of the bis(mu-oxo) isomer. The peroxo complex was characterized by UV-vis and resonance Raman spectroscopy, as well as an X-ray crystal structure (albeit of marginal quality due to disorder problems). Intramolecular attack at the alpha C-H bonds of the substituents was indicated as the primary decomposition pathway of the oxygenated compounds through examination of the decay kinetics and the reaction products, which included bis(mu-hydroxo)- and mu-carbonato-dicopper complexes that were characterized by X-ray diffraction. A rationale for the varying results of the oxygenation reactions was provided by analysis of (a) the X-ray crystal structures and electrochemical behavior of the Cu(I) precursors and (b) the results of theoretical calculations of the complete oxygenated complexes, including all ligand atoms, using combined quantum chemical/molecular mechanics (integrated molecular orbital molecular mechanics, IMOMM) methods. The size of the ligand substituents was shown to be a key factor in controlling the relative stabilities of the peroxo and bis(mu-oxo) forms, and the nature of this influence was shown by both theory and experiment to depend on the ligand macrocycle ring size.     

Antimony and silicon environments in antimony silicate glasses

Antimony silicate glasses, of general formula xSb₂O₃·(1−x)SiO₂ (0.1≤x≤0.78), have been prepared by melt-quenching and their structures studied using ²⁹Si MAS NMR spectroscopy, ¹²¹Sb Mössbauer spectroscopy and Raman spectroscopy. Oxidation during melting gives rise to Sb⁵⁺ in concentrations, which increase linearly with x to give a value of ∼10% when x=0.78. ¹²¹Sb Mössbauer spectra show Mössbauer shifts and quadrupole splittings consistent with Sb³⁺ in a [:SbO₃] trigonal pyramid, similar to that in crystalline Sb₂O₃. A broad band in the Raman spectrum at ∼410 cm⁻¹ is due to the vibrations of such a unit. The dependence of the silicon Qⁿ speciation on x can be interpreted by the formation of Sb-O-Sb links possibly to form rings of 4 [:SbO₃] units such as are found in valentinite.     

Plutonium metal standards exchange program for actinide measurement quality assurance (2001–2007)

Plutonium metal exchange programs operated by the Rocky Flats Plant were conducted from 1956–1989 to ensure quality and to compare measurements in a plutonium metal matrix. Los Alamos National Laboratory (LANL) re-established the program in 2001 to assess the quality of analytical chemistry capabilities that support special nuclear material characterization. It is the only program of its kind for the preparation and distribution of plutonium metal reference materials with a range of impurity contents to multiple laboratories for destructive measurements of elemental concentration, isotopic abundance, and both metallic and non-metallic impurity levels. This program provides independent verification of analytical measurement capabilities for each of the seven currently participating laboratories, and allows any technical problems with analytical measurements to be identified and corrected. This paper focuses on basic program elements and presents a summary of methods and results for plutonium, uranium, neptunium, and americium, measurements.     

Desymmetrization of a centrosymmetric diepoxide: efficient synthesis of a key intermediate in a total synthesis of hemibrevetoxin B

The preparation of an established intermediate in a total synthesis of hemibrevetoxin B is described. The acid-catalyzed cyclization of trans-4,5-epoxyoctane-2,7-dione exhibited a valuable mixture of kinetic and thermodynamic control: stereospecific epoxide opening was followed by equilibration of the products to provide the required trans-fused octahydropyrano[3,2-b]pyran ring system. Two-directional elaboration, by acetal substitution, ozonolysis, and sulfur ylide-mediated epoxidation, provided a centrosymmetric diepoxide. The key step of the synthesis was the first desymmetrization of a centrosymmetric molecule in natural product synthesis: Jacobsen asymmetric epoxide hydrolysis and acetonization provided the known synthetic intermediate in 97% yield and >95% ee over two steps. The exploitation of the center of symmetry of the AB ring system of the natural product contributed greatly to the efficiency (eight steps, 34% overall yield) of the synthesis.