Molecular structures of dicarboxylated viologens on a Cu(100) surface during an ongoing charge transfer reaction

Molecular structures of dicarboxylated viologens (1,1'-bis (7-carboxyheptyl)-4,4'-bipyridinium dibromide molecules, V-(C(7)-COOH)(2)) on a Cu(100) surface are studied by means of in situ scanning tunneling microscopy (STM) in combination with cyclic voltammetry (CV). Self-assembled monolayers of adsorbed dicarboxylated viologens form during an ongoing charge transfer reaction. Mainly six structures of the organic molecules are observed, including a dot array, metastable phases, stripe patterns, a closed stacking stripe pattern, chloride desorption, and a dimer phase. The molecular structural models for all the structures have been successfully established. The carboxylated viologen molecules in the dicationic state prefer the face-on configuration on the surface and form the dot array phase. The other phases are shown by the radical state of the viologens. The metastable phases show two forms: cluster-like and stripe pattern-like structures. Main features of the metastable phases are face-to-face configurations of the radical viologens in π-stacking form between neighboring parallel bipyridiniums. Hydrogen bonding is considered to be the major factor in constructing the network of the stripe pattern. At a more negative potential, the bilayers of the stripe pattern transform to be a monolayer of the closed stacking stripe pattern because of the enhanced electrostatic force. The closed stacking stripe pattern is stable on the surface until chloride desorption. As the chloride anions desorb from the Cu(100) surface, the disordered dimers transform to an ordered dimer phase on a Cu(100)-1×1 surface due to the hydrogen bonding between neighboring dimer rows.     

Strain-reduced GaN thick-film grown by hydride vapor phase epitaxy utilizing dot air-bridged structure

A 300 μm GaN thick-film, in diameter 1.5 in, was demonstrated without any crack by hydride vapor phase epitaxy (HVPE) growth. The technique used in relaxing the residual stress caused by differences of thermal expansion coefficients (TEC) and lattice constants between GaN and sapphire substrate to prevent GaN film from crack is called a dot air-bridged structure. After the laser lift-off process, 300-μm-thick freestanding GaN wafer, in diameter 1.5 in, could be fabricated. The compressive stress in the dot air-bridged structure was measured by micro-Raman spectroscopy with the E₂(high) phonon mode. The compressive stress could be reduced to as small as 0.04 GPa, which could prevent the crack during the epitaxial process for GaN growth by HVPE. It is important to obtain a large-area crack-free GaN thick-film, which can be used for fabricating freestanding GaN wafer.     

Pt-chain induced formation of Ge nanowires on the Ge(001) surface

A new reconstructed Pt/Ge(001)–4 × 2 surface structure of 0.25 ML Pt deposition is suggested based on density functional theory. The Ge dimers form nanowire arrays on a Pt-chain modified Ge(001) surface in which the chain is located between the two quasi-dimer rows and below the Ge nanowire. The simulated scanning tunneling microscope (STM) images of the surface are in excellent agreement with the previously observed STM features and sample bias dependence. It is the nanowire Ge dimers and not the Pt atoms that contribute to the STM images for occupied states at high sample biases, contrary to what has always been assumed in experiments. The surface bands of the Pt chain and quasi-dimer rows exhibit quasi-one-dimensional metallic behavior in the direction of the nanowire. When changing from the 4 × 2 to the 4 × 4 structure, there are likely pseudogaps opened at the new surface Brillouin zone boundary, which simultaneously reduce the metallicity. This may be related to the Peierls instability. The interaction between the Pt chain and the quasi-dimer row, as well as the inter-quasi-dimer row interaction, is of essential importance for stabilization.     

Atomic and electronic structures of thin NaCl films grown on a Ge(0 0 1) surface

Density functional theory (DFT) with LDA and GGA have been employed to study the interface and thin film properties of NaCl on a Ge(0 0 1) surface. The atomic and electronic structures of thin NaCl films from one to ten monolayers were analyzed. The layer adsorption energies show that a quasi-crystalline (0 0 1) fcc NaCl film is built up via a layer-by-layer growth mode with NaCl thickness above 2 ML. Simulated STM images show a well-resolved (1 × 1) NaCl atomic structure for sample bias voltage V_s < −2.5 V and the bright protrusions should be assigned to the Cl⁻ ions of the NaCl film. The Ge substrate dimer is reserved and buckled like a clean Ge(0 0 1)-p(2 × 2) surface as the result of weak interface interaction between the dangling bonds coming from valence π states of the Ge substrate and the 3p states of the interfacial Cl⁻ ion. These results are consistent with the experiments of STM, LEED and EELS.     

Development of a 4–15 μm infrared GaAs hyperspectral QWIP imager

In the on-going evolution of GaAs quantum well infrared photodetectors (QWIPs) we have developed a four band, 640 × 512, 23 μm × 23 μm pixel array which we have subsequently integrated with a linear variable etalon (LVE) filter providing over 200 spectral bands across the 4–15.4 μm wavelength region. This effort was a collaboration between NASA’s Goddard Space Flight Center (GSFC), the Jet Propulsion Laboratory (JPL) and the Army Research Laboratory (ARL) sponsored by the Earth Science Technology Office of NASA. The QWIP array was fabricated by graded molecular beam epitaxial (MBE) growth that was specifically tailored to yield four distinct bands (FWHM): Band 1; 4.5–5.7 μm, Band 2; 8.5–10 μm, Band 3; 10–12 μm and Band 4; 13.3–14.8 μm. Each band occupies a swath that comprises 128 × 640 elements. The addition of the LVE (which is placed directly over the array) further divides the four “broad” bands into 209 separate spectral bands ranging in width from 0.02 μm at 5 μm to 0.05 μm at 15 μm. The detector is cooled by a mechanical cryocooler to 46 K. The camera system is a fully reflective, f/4.2, 3-mirror system with a 21° × 25° field of view. The project goals were: (1) develop the 4 band GaAs QWIP array; (2) develop the LVE and; (3) implement a mechanical cryocooler. This paper will describe the efforts and results of this undertaking with emphasis on the overall system characteristics.     

Syntheses of New Isocephems and Isodethiaoxacephems as Antimicrobial Agents

The cis-configurated isocephem 26 as well as isodethiaoxacephems 21 and 33 were synthesized (Schemes 4 and 5). The key step involves chlorination of the corresponding carbanions of 23, 18 , and 31 with CF₃SO₂Cl followed by internal alkylation. β-Lactams 3, 21, 26 , and 33 were found to possess biological activity against several pathogenic microorganisms in vitro. Electronic activation of the lactam moiety in isodethiaoxacephem 33 remarkably enhanced its biological activity.