Electronic structure,Compton profiles and optical properties of TaC and TaN

Isotropic Compton profiles of TaC and TaN have been measured for the first time, at an intermediate resolution, using 662 keV γ-radiation. Energy bands, density of states and Fermi surface topology of TaC and TaN have been computed using linear combination of atomic orbitals with density functional theory and full potential linearised augmented plane wave method. Both band structure calculations predict the metallic character of TaC and TaN. The electron momentum densities calculated using various approaches of density functional theory are compared with the present measurements. On the basis of Mulliken’s population, it is also seen that TaC has more covalent bonding than TaN. The optical properties computed using full potential linearised augmented plane wave method are explained in terms of intraband transitions.     

Structural diversity of peroxidase-catalyzed oxidation products of o-methoxyphenols

[reaction: see text] The biocatalytic oxidation of o-methoxyphenolic compounds led to a variety of oligophenols (dimers to pentamers) and some of their oxidation products. The reaction was carried out in an aqueous medium at room temperature with hydrogen peroxide as the terminal oxidant in a facile and green route to potentially bioactive compounds. Detailed structural information on the products of peroxidase-catalyzed oxidation of o-methoxyphenols is presented for the first time.     

Mitigating repulsions in close quarters: Copper tells us how!

Four copper(I) complexes of short bite ligands, bis(diphenylphosphino)amine (dppa) and bis(diphenylphosphino)isopropylamine (dppipa) were synthesized from appropriate precursors. All complexes were characterized by single crystal X-ray crystallography and spectroscopic techniques. In each of these complexes, two filled shell cations are forced into close proximity (≈2.7–2.8 Å). With no strong π acid ligands to siphon electron density from the filled d shell, the unavoidable repulsive d¹⁰–d¹⁰ interaction is mitigated when an unsymmetrical coordination environment around the copper atoms exists. The coordinatively saturated copper ion functions as a donor to the coordinatively unsaturated copper. A Cambridge Structural Database (CSD) search reveals the greater propensity of clusters with short contacts to adopt unsymmetrical coordination.     

ESPT of 2-(2'-pyridyl)benzimidazole at the Micelle-Water interface: selective enhancement and slow dynamics with sodium dodecyl sulfate

The effect of micellar environment on the excited state proton transfer (ESPT) of 2-(2'-pyridyl)benzimidazole (2PBI) has been investigated by steady state and time resolved fluorescence spectroscopy. The ESPT, which occurs to a rather small extent at pH 7, is found to be enhanced remarkably at the interface of sodium dodecyl sulfate (SDS) micelles and water. Such an enhancement is not observed for the cationic cetyl trimethyl ammonium bromide (CTAB) or neutral Triton X-100 micelles. This selective enhancement is explained in the light of a modification of pK(a) and a more acidic local pH in the micelle-water interface. A rise time of about 890 ps is observed in the region of tautomer emission. The origin of this rise time is explored, considering three factors, namely, diffusion controlled protonation of the normal form of 2PBI, slow and possibly incomplete solvation of the transition state, leading to a slowing down of the proton transfer process and a similar slow dynamics of the tautomeric excited state.     

A compton profile study of tantalum

We report the results of Compton profile study on polycrystalline tantalum. Measurements have been made using 59.54 keV gamma-rays. The results are compared with the APW band structure calculations of Papanicolaouet al and other available data. In contrast to the work of Changet al the overall agreement is better with the APW band structure which worsens on incorporating the electron correlation correction. Estimates of the errors due to the contribution from bremsstrahlung, non-validity of impulse-approximation and anomalous dispersion are also briefly discussed.     

Compton profile of molybdenum

In this paper we report the experimental Compton profile of polycrystalline molybdenum. The measurements have been made by scattering 59.54 keVγ-rays and are compared with the recent band structure calculation of Janiet al. [4]. These results have also been compared with our calculation based on the renormalized-free-atom model for different 4d-5s configurations. It is found that the present experimental data are relatively in good agreement with the band structure calculation.     

Probability-one homotopy maps for mixed complementarity problems

Probability-one homotopy algorithms have strong convergence characteristics under mild assumptions. Such algorithms for mixed complementarity problems (MCPs) have potentially wide impact because MCPs are pervasive in science and engineering. A probability-one homotopy algorithm for MCPs was developed earlier by Billups and Watson based on the default homotopy mapping. This algorithm had guaranteed global convergence under some mild conditions, and was able to solve most of the MCPs from the MCPLIB test library. This paper extends that work by presenting some other homotopy mappings, enabling the solution of all the remaining problems from MCPLIB. The homotopy maps employed are the Newton homotopy and homotopy parameter embeddings.     

On a low intensity <Superscript>241</Superscript>Am Compton spectrometer for measurement of electron momentum density

In this paper, a new design and construction of a low intensity (100 mCi) ²⁴¹Am γ-ray Compton spectrometer is presented. The planar spectrometer is based on a small disc source with the shortest geometry. Measurement of the momentum density of polycrystalline Al is used to evaluate the performance of the new design. The measured profile is in good agreement with the existing theoretical data and our density functional calculations.      

Gallium and indium under high pressure

Ga and In crystallize in unusual open ground-state crystal structures. Recent experiments have discovered that Ga under high pressure transforms into a close-packed structure, while this has so far not been observed for In. Results from first principles calculations explain in a simple way this difference in behavior. We predict a so far undiscovered transition of In to a close-packed structure at extreme pressures and show that the structure determining mechanism originates from the degree of s-p mixing of the valence orbitals. Group-III elements are shown to strongly disobey the standard corresponding-state rule.     

Generation of desired signals from acoustic drivers

A general but systematic procedure has been developed to control transient signal generation for the study of internal noise propagation from aircraft engines. Transform techniques are used in a simple algorithm to produce signals—pulses in this study—of any desired waveform from acoustic drivers. By a judicious input, the accurate driver response function is calculated. From the driver response function the limiting frequency characteristics are determined. The undesirable frequencies where the driver response is poor are eliminated from the analysis. The inverse of the response function is then convolved with the desired signal to produce a synthesized signal. The shape of the synthesized signal is in general quite awkward, in both the time and the frequency domain. Nevertheless, when the distorted signal is fed into the driver, the driver generates the desired signal. The driver is operated in two environments—in a free field and in a duct—and results are presented to show the impedance matching effect of the driver. A set of results with a high frequency cut-off value as a parameter is given to demonstrate the extent of the applicability of the synthesis procedure. The error in the numerical inversion is highlighted. The results show that, within the imposed guidelines, it is possible to generate desired signals through the signal synthesis procedure.