Indo-Mo Model with s·p Separation

A newly developed self-consistent-field molecular orbital theory is described and tested. The intermediate neglect of differential overlap (INDO) approximation is used, and all interaction integrals are differentiated according to their dependence upon 2s and 2p AO's. The bonding parameter β_l is reformulated so that the model is calibrated to only one specific molecular property, namely, the ionization energy of Hi. We expect that this model will not be biased toward any special families of molecules.     

Synthesis and luminescence properties of U-shaped polycyclic molecules containing syn-facial functionalized quinoxaline rings

[reaction: see text] Rigid U-shaped molecules containing syn-facially situated quinoxaline rings have been synthesized in three steps, by a combination of the Diels-Alder reaction, the ruthenium-catalyzed oxidation, and the Zn(OAc)(2)-catalyzed condensation of the resulting bis-alpha-diketones with benzene-1,2-diamines. The unsymmetric bis-quinoxalines, with electronically different substituents, and the quinoxaline ring-attached alpha-diketones were also prepared. Their luminescence properties were examined and described.     

Electrolithographic investigations of the hydrophilic channels in Nafion membranes

Nafion membranes are used as semisolid electrolytes in methanol and hydrogen fuel cells. The ion conduction takes place through those hydrophilic channels in the Nafion that can provide continuous pathways through the membrane. There is as yet limited information about the density, the size, and the shape of these channels. We have developed two electrochemical methods of visualizing the pore structure which involve the creation of metal lithographs using the membrane pores as templates. In the experiments, the membrane is supported on a flat solid surface on one side, and is in contact with an electrolyte on the other side. Using hydrogen-terminated n-doped Si(111), we deposited gold from an electrolyte containing a gold salt. The Au ions traverse the membrane through the pores, reach the silicon surface, and are spontaneously reduced. A metallic Au deposit is formed on the silicon surface, at the base of the hydrophilic channel. The Au deposits are imaged after the membrane is dissolved. Another method involves supporting the membrane on a Pt surface and depositing silver wires through the hydrophilic channels of the membrane. The scanning electron microscope pictures of these wires provide an image of the size and the shape of the hydrophilic channels.     

Hydrogenation-induced insulating state in the intermetallic compound LaMg2Ni

Hydrogenation-induced metal-semiconductor transitions usually occur in simple systems based on rare earths and/or magnesium, accompanied by major reconstructions of the metal host (atom shifts >2 A). We report on the first such transition in a quaternary system based on a transition element. Metallic LaMg2Ni absorbs hydrogen near ambient conditions, forming the nonmetallic hydride LaMg2NiH7 which has a nearly unchanged metal host structure (atom shifts <0.7 A). The transition is induced by a charge transfer of conduction electrons into tetrahedral [NiH4]4- complexes having closed-shell electron configurations.     

Thermal stability and electronic structure of atomically uniform Pb films on Si(111)

Atomically uniform Pb films are successfully prepared on Si(111), despite a large lattice mismatch. Angle-resolved photoemission measurements of the electronic structure show layer-resolved quantum well states which can be correlated with dramatic variations in thermal stability. The odd film thicknesses N = 5, 7, and 9 monolayers show sharp quantum well states. The even film thicknesses N = 6 and 8 do not, but are much more stable than the odd film thicknesses. This correlation is discussed in terms of a total energy calculation and Friedel-like oscillations in properties.     

Spin dynamics in the carrier-doped S=1/2 triangular lattice of NaxCoO2.yH2O

We probed the local electronic properties of the mixed-valent Co+4-x triangular lattice in NaxCoO2.yH(2)O by 59Co NMR. We observed two distinct types of Co sites for x > or =1/2, but the valence seems averaged out for x approximately 1/3. Local spin fluctuations exhibit qualitatively the same trend down to approximately 100 K regardless of the carrier concentration x, and hence the nature of the electronic ground state. A canonical Fermi-liquid behavior emerges below approximately 100 K only for x approximately 1/3.     

Determining the hydrographic parameters of the surface of water from the image sequences of a CCD camera

Water surface fluctuations were analyzed using image sequences from a CCD (charge coupled device) camera. Both regular and irregular waves were used for the study. A transfer function is obtained by comparing the gray scales of the image and results of in-situ wave gauge array measurements. The effects of non-uniform illumination within the wave basin are imbedded in the transfer function. Thus, the obtained transfer function is directly applicable to all other areas of interests within the wave basin. Estimated wave heights are all in qualitative agreement with those obtained through direct measurements. It is shown that the averaged relative error between these two wave heights is less than 16%.     

Alternating layer and island growth of Pb on Si by spontaneous quantum phase separation

Real-time in situ x-ray studies of continuous Pb deposition on Si(111)-(7x7) at 180 K reveal an unusual growth behavior. A wetting layer forms first to cover the entire surface. Then islands of a fairly uniform height of about five monolayers form on top of the wetting layer and grow to fill the surface. The growth then switches to a layer-by-layer mode upon further deposition. This behavior of alternating layer and island growth can be attributed to spontaneous quantum phase separation based on a first-principles calculation of the system energy.     

Improved direct measurement of the parity-violation parameter Ab using a mass tag and momentum-weighted track charge

We present an improved direct measurement of the parity-violation parameter A(b) in the Z boson-b-quark coupling using a self-calibrating track-charge technique applied to a sample enriched in Z-->bb events via the topological reconstruction of the B hadron mass. Manipulation of the Stanford Linear Collider electron-beam polarization permits the measurement of A(b) to be made independently of other Z-pole coupling parameters. From the 1996-1998 sample of 400,000 hadronic Z decays, produced with an average beam polarization of 73.4%, we find A(b)=0.906+/-0.022(stat)+/-0.023(syst).     

Synthesis and characterization of luminescent osmium(II) carbonyl complexes based on chelating dibenzoylmethanate and halide ligands

Octahedral Os(II) complexes 1-5 with formula [Os(CO)3X(dbm)] are prepared through utilization of both solid-state pyrolysis and ligand exchange reactions. These complexes exhibit prominent 3pi-pi* phosphorescence with unusually long lifetimes (29-64 micros) and high quantum yields (0.08-0.13).