Electronic-structures of h2o.bf3 and related n-v addition-compounds - a combined eels-ups study in vapor-phase

The detailed electronic structure of the n-v addition compound H2O·BF3 has been investigated for the first time by a combined use of electron energy loss spectroscopy (EELS) and UV photoelectron spectroscopy (UPS) augmented by MO calculations. The calculated molecular orbital energies of H2O·BF3 agree well with the UPS results and have been used to assign the electronic transitions obtained from EELS and to construct an orbital correlation diagram. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.

A laser flash photolysis study of pivalothiophenone triplets: steric and electronic effects in thione photoreaction kinetics

Upon laser pulse excitation (Aex = 532 nm) into the lowest-lying '(n,a*) band system, pivalothiophenones in benzene solutions give rise to short-lived triplets (Ama: = 325-335 nm, em: = (1 1-15) X lo3 M-' cm-I) with quantitative intersystem crossing efficiencies. The triplet yields decrease slightly (by 10-30%) upon changing A, to 308 nm (Le., upon excitation into S2). Kinetic data are presented for intrinsic triplet lifetimes, self-quenching, and quenching by oxygen, di-tert-butylnitroxy radical, and various reagents capable of interacting with the triplets via energy, electron, or hydrogen-atom transfer and by biradical formation (possibly leading to cycloaddition). The mechanisms of the quenching processes are discussed. Relative to rigid aromatic thiones, namely, xanthione and thiocoumarin, the interaction of pivalothiophenone triplets with most of the quenchers are kinetically inefficient. This is interpreted primarily as a manifestation of the steric crowding at positions a to the thiocarbonyl group.

Wideband acoustic absorption characteristics of rubberized coir for underwater applications

Reflection and transmission coefficients of rubberized coir pads over the frequency band 200 kHz to 4 MHz are presented in this Paper. These results are compared with those reported for neoprene, paraffin wax, rubber car mat and plastic door mat1. The rubberized coir pads were found to possess wideband absorption characteristics. It has been experimentally found that 0.05 m thick coir pads have almost 100% absorption in the frequency range 800 kHz-3 MHz with a maximum at 2.35 MHz. We have used this material for lining the water tank for underwater acoustic studies.

Absorption of electromagnetic radiation by superconducting YBa2Cu3O7: an oxygen-induced phenomenon

In the superconducting state, YBa2Cu3O7 absorbs electromagnetic radiation over a wide range of frequencies (8 MHz-9 GHz). The absorption is extremely sensitive to temperature, particle size and the magnetic field and depends crucially on the presence of oxygen. A possible explanation for the phenomenon based on the formation of Josephson junctions is suggested.

Ultrasonic attenuation in strongly disordered electronic systems

The attenuation of long-wavelength phonons due to their interaction with electronic excitations in disordered systems is investigated here. Lattice strain couples to electronic stress, and thus ultrasonic attenuation measures electronic viscosity. The enhancement and critical divergence of electronic viscosity due to localization effects is calculated for the first time. Experimental consequences for the anomalous increase of ultrasonic attenuation in disordered metals close to the metal-insulator transition are discussed. In the localized regime, the appropriate model is one of electronic two-level systems (TLS’s) coupled to phonons. The TLS consists of a pair of states with one localized state occupied and the other unoccupied. The density of such low-excitation-energy TLS’s is nonzero due to long-range Coulomb interactions. The question of whether these could be significant low-energy excitations in glasses is touched upon.

X-ray absorption spectra of niobium dichalcogenides and their first-row transition-metal intercalates

X-ra!. K-absorption spectra of niobium in niobium dichalcogenides. namely NbS, and NbSe, and their first-row transition-metal intercalates Mi P 3N bSz (M = Cr. Mn. Fe. Co. Ni) and Ml#,NbSe2 (M = Fe. CO). have been measured together with those in niobium metal. The spectra of these materials are \er? similar to one another. They reflect the transitions to the partially filled niobium d band with some p character. A bariety of x-ray absorption nearedge structures (XASES) associated with the K edges of intercalated atoms are also presented and discussed.

Photochemical Oxidation of Thioketones: Steric and Electronic Aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts. A zwitterionic/ diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine. While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine. This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

Photochemical oxidation of thio ketones: steric and electronic aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts. A zwitterionic/ diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine. While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine. This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

Study of strontium compounds and minerals by X-ray absorption spectroscopy. I. K-edge shifts

The chemical shifts in the X-ray K-absorption edge of strontium in various compounds and in six minerals are measured using a single crystal X-ray spectrometer. Besides valence, the shifts are found to be governed by ionic charges on the absorbing ions, which are calculated employing Pauling's method. For the minerals the plot of chemical shift against the theoretically calculated ionic charges is used to determine the charges on the strontium ions.

Interaction of rat testis protein, TP, with nucleic acids in vitro. Fluorescence quenching, UV absorption, and thermal denaturation studies

The nucleic acid binding properties of the testis protein, TP, were studied with the help of physical techniques, namely, fluorescence quenching, UV difference absorption spectroscopy, and thermal melting. Results of quenching of tyrosine fluorescence of TP upon its binding to double-stranded and denatured rat liver nucleosome core DNA and poly(rA) suggest that the tyrosine residues of TP interact/intercalate with the bases of these nucleic acids. From the fluorescence quenching data, obtained at 50 mM NaCl concentration, the apparent association constants for binding of TP to native and denatured DNA and poly(rA) were calculated to be 4.4 X 10(3) M-1, 2.86 X 10(4) M-1, and 8.5 X 10(4) M-1, respectively. UV difference absorption spectra upon TP binding to poly(rA) and rat liver core DNA showed a TP-induced hyperchromicity at 260 nm which is suggestive of local melting of poly(rA) and DNA. The results from thermal melting studies of binding of TP to calf thymus DNA at 1 mM NaCl as well as 50 mM NaCl showed that although at 1 mM NaCl TP brings about a slight stabilization of the DNA against thermal melting, a destabilization of the DNA was observed at 50 mM NaCl. From these results it is concluded that TP, having a higher affinity for single-stranded nucleic acids, destabilizes double- stranded DNA, thus behaving like a DNA-melting protein.

Electron energy loss spectroscopy (EELS) of H2O, H2S, H2Se and H2Te

Electronic excitation in H2O, H2S, H2Se and H2Te molecules has been studied by the EELS technique. Spectra of H2S and H2Se are remarkably similar with the 1b1-nd transition most intense. The intensity of the first transition 1b1-nsa1 decreases through H2O to H2Se and this transition is absent in H2Te. Transitions observed by EELS have been compared with optical absorption studies. A correlation diagram of the occupied and the excited states has been provided for these four molecules by making use of UVPES and EELS.

Pressure-induced electronic and structural transformations in bulk gese2 glass

The pressure dependence of the electrical of the electrical resistivity of bulk GeSe2 glass shows a semiconductor-to-metal transition at 7 GPa pressure. The high pressure phase is examined using he x-ray diffractometer and is found to be crystalline, with a face-centered cubic structure having a =4.06A. The electrical conductivity has also been studied as a function of temperature at various pressures.

Surface electronic structure of the high-Tc oxides

Electron energy loss spectroscopy (EELS) has been employed to monitor surface conductivity changes in YBa2Cu3O7 as a function of temperature. Concomitant use of x-ray photoelectron spectroscopy (XPS) establishes that the formation of oxygen dimers with lowering of temperature is accompanied by a simultaneous increase of surface conductivity.

Preparation, structure, microwave absorption and other properties of the 125K superconductor Tl2Ca2Ba2Cu3O10+δ*1

It is shown that Tl2Ca2Ba2Cu3O10+δ (2223), the n=3 member of the Tl2O2. Can�1Ba2CunO2n+2 family shows a Tc (zero-resistance) of 125K (onset 140K) only when it is prepared by the sealed tube ceramic method starting from the 1313 composition. The structure is orthorhombic (Image compared to 30� of 2122), but electron diffraction patterns show two possible orthorhombic structures. Lattice images show the expected local structure and also the presence of dislocations and intergrowths. Both 2223 and 2122 oxides absorb microwaves (9.1GHz) intensely in the superconducting state, with some hysteresis. XPS measurements show Cu mainly in the 1+ state, suggesting the important role of oxygen holes.

Chlorinated Hypoelectronic Dimetallaborane Clusters: Synthesis, Characterization, and Electronic Structures of (eta(5)-C5Me5W)(2)B5HnClm (n=7, m=2 and n=8, m=1)

Pyrolysis of (eta(5)-C5Me5WH3)B4H8, 1, in the presence of excess BHCl2 center dot SMe2 in toluene at 100 degrees C led to the isolation of (eta(5)-C5Me5W)(2)B5H9, 2, and B-Cl inserted (eta(5)-C5Me5W)(2)B5H8Cl, 3, and (eta(5)-C5Me5W)(2)B5H7Cl2, (four isomers). All the Chlorinated tungstaboranes were isolated as red and air and moisture sensitive solids. These new compounds have been characterized in solution by H-1, B-11, C-13 NMR, and the structural types were unequivocally established by crystallographic analysis of compounds 3, 4, and 7. Density functional theory (DFT) calculations were carded out on the model molecules of 3-7 to elucidate the actual electronic structures of these chlorinated species. On grounds of DFT calculations we demonstrated the role of transition metals, bridging hydrogens, and the effect of electrophilic substitution of hydrogens at B-H vertices of metallaborane structures.