The low frequency behaviour in high frequency capacitance–voltage characteristics due to contribution of band-to-band tunnelling and generation–recombination in Hg0.75Cd0.25Te MIS capacitors

Hg_1−xCd_xTe Metal–Insulator–Semiconductor (MIS) capacitors were studied both experimentally and theoretically to investigate the capacitance contributions due to band-to-band (btb) tunnelling and generation–recombination (gr) of carriers to inversion layer capacitance. A good fit to the data has been obtained by including the btb contributions rather than gr contributions.     

Complex impedance spectroscopy of Mn-doped zinc oxide nanorod films

The frequency-dependent properties of Mn-doped (3-5 at.%) aligned zinc oxide (Mn-ZnO) nanorods, synthesized by hybrid wet chemical route onto glass substrates, were investigated by bias-dependent impedance spectroscopy. No peak of Mn cluster/secondary phases was detected in the X-ray diffraction traces of the samples. XPS studies show the presence of oxygen vacancies in Mn-ZnO nanorods and Mn in Mn²⁺ and Mn⁴⁺ charge states. Although X-ray diffraction/X-ray photoelectron spectroscopy does not give any indication of the presence of metal clusters in the samples, bias-dependent impedance spectroscopy demonstrates significant sensitivity to the formation of Mn clusters in Mn-ZnO nanorods.     

Surface reconstruction and decahedral structure of bimetallic nanoparticles

We report on energetic surface reconstruction phenomena observed on bimetallic nanoparticle systems of AuPd and AuCu, similar to a resolidification effect observed during the cooling process in lead clusters. These binary alloy nanoparticles show the fivefold edges truncated, resulting in [100] facets on decahedral structures, an effect largely envisioned and reported theoretically, with no experimental evidence so far. We demonstrate experimentally as well as by computational simulations that this new eutectic structure is favored in such nanoalloy systems.     

Pseudogap behavior in Pr0.5Sr0.5MnO3: A photoemission study

The valence band electronic structure of Pr_0.5Sr_0.5MnO₃ has been investigated across its paramagnetic metallic (PMM)–ferromagnetic metallic (FMM)–antiferromagnetic insulator (AFMI) transition. Using surface sensitive high resolution photoemission we have conclusively demonstrated the presence of a pseudogap of magnitude 80 meV in the near Fermi level electronic spectrum in the PMM and FMM phases and finite intensity at the Fermi level in the charge ordering (CO)-AFMI phase. The pseudogap behavior is explained in terms of the strong electron–phonon interaction and the formation of Jahn Teller (JT) polarons, indicating the charge localizations. The finite intensity at the Fermi level in the insulating phase showed a lack of charge ordering in the surface of the Pr_0.5Sr_0.5MnO₃ samples.     

A conceptual high flux reactor design with scope for use in ADS applications

A 100 MWt reactor design has been conceived to support flux level of the order of 10¹⁵ n/cm²/s in selected flux trap zones. The physics design considers high enriched metallic alloy fuel in the form of annular plates placed in a D₂O moderator tank in a hexagonal lattice arrangement. By choosing a tight lattice pitch in the central region and double the lattice pitch in the outer region, it is possible to have both high fast flux and thermal flux trap zones. By design the flux level in the seed fuel has been kept lower than in the high flux trap zones so that the burning rate of the seed is reduced. Another important objective of the design is to maximize the time interval of refueling. As against a typical refueling interval of a few weeks in such high flux reactor cores, it is desired to maximize this period to as much as six months or even one year. This is possible to achieve by eliminating the conventional control absorbers and replacing them with a suitable amount of fertile material loading in the reactor. Requisite number of seedless thorium-aluminum alloy plates are placed at regular lattice locations vacated by seed fuel in alternate fuel layers. It is seen that these thorium plates are capable of acquiring asymptotic fissile content of 14 g/kg in about 100 days of irradiation at a flux level of 8 × 10¹⁴ n/cm²/s. In summary, the core has a relatively higher fast flux in the central region and high thermal flux in the outer region. The present physics design envisages a flat core excess reactivity for the longest possible cycle length of 6 months to one year. It is also possible to modify the design for constant subcriticality for about the same period or longer duration by considering neutron spallation source at the centre and curtailing the power density in the inner core region by shielding it with a layer of thoria fuel loading.      

Order–disorder transition in nanocrystalline Ni3Al prepared by a chemical route

Ni₃Al alloys of nanometer dimensions in the range 10–38 nm could be synthesized by reaction sintering of sol–gel-derived Ni/SiO₂ nanocomposite and commercially available micrometer-sized aluminum powder. The sintering was carried out at a temperature of 923 K and a pressure of 2.4 MPa. By a suitable choice of sintering conditions a disordered phase of Ni₃Al was stabilized. The disordered phase could be converted to an ordered one by an increase of heat treatment temperature.     

A combined treatment of hydration and dynamical effects for the modeling of host–guest binding thermodynamics: the SAMPL5 blinded challenge

As part of the SAMPL5 blinded experiment, we computed the absolute binding free energies of 22 host–guest complexes employing a novel approach based on the BEDAM single-decoupling alchemical free energy protocol with parallel replica exchange conformational sampling and the AGBNP2 implicit solvation model specifically customized to treat the effect of water displacement as modeled by the Hydration Site Analysis method with explicit solvation. Initial predictions were affected by the lack of treatment of ionic charge screening, which is very significant for these highly charged hosts, and resulted in poor relative ranking of negatively versus positively charged guests. Binding free energies obtained with Debye–Hückel treatment of salt effects were in good agreement with experimental measurements. Water displacement effects contributed favorably and very significantly to the observed binding affinities; without it, the modeling predictions would have grossly underestimated binding. The work validates the implicit/explicit solvation approach employed here and it shows that comprehensive physical models can be effective at predicting binding affinities of molecular complexes requiring accurate treatment of conformational dynamics and hydration.     

Physicochemical studies on bioactive Cr(III) coordination compounds with esters of hydrazine carboxylic acid as hetero donor ligands

Reaction between hydrazine derivative ligands (HrzE) or (HrzB) and chromium salt in 1:2 (metal:ligand) molar ratio yielded monometallic trivalent coordination compounds with general formula [Cr(HrzE)₂X₂]X and [Cr(HrzB)₂X₂]X, where (HrzE) = hydrazine carboxylic acid ethyl ester, (HrzB) = hydrazine carboxylic acid tert-butyl ester, and X = Cl^?, Br^? or F^?. Elemental analysis, conductivity measurements, magnetic moment measurements, and various spectroscopic techniques, viz. infrared, ultraviolet–visible, and electrospray ionization mass spectrometry, were applied to illustrate the structure and composition of the coordination compounds. Analytic and conductivity results were consistent with 1:1 electrolytic behavior and the proposed formulas of the coordination compounds. Electronic absorption data and magnetic moment parameters indicated octahedral geometry surrounding the metal ion in the coordination compounds. The in vitro antimicrobial behavior of the ligands and coordination compounds was screened using four bacterial strains (Staphylococcus aureus, Bacillus subtilis, Escherichia coli, and Salmonella typhi) and two fungal strains (Candida parapsilosis and Saccharomyces cerevisiae). The results indicated improved activity of the coordination compounds compared with the free ligands against the studied bacteria and fungi.     

Diaminodithioether complexes of nickel(II) and palladium(II): A unique case of dealkylation of S,S′-thioether

Summary Nickel(II) and palladium(II) complexes of the 1,3-di(o-aminophenylthio) propane (H₂L¹) and 1,2-di(o-aminophenylthio)xylene (H₂L²) ligands have been prepared and characterized. The hydrobromide salt of H₂L¹ gave a 12 ligand-metal complex of Pd^II, whereas free H₂L¹ formed the usual 1:1 species. The reaction of Na₂PdCl₄ with H₂L² resulted in S,S-dealkylation of the ligand and formation of a mononuclear complex of the corresponding thiol, i.e. 2-aminobenzenethiol. NiCl₂, NiBr₂ and Ni(ClO₄)₂ did not react directly with H₂L². Ni^II is a fairly hard ion and therefore does not coordinate to the soft thioether moiety in H₂L² in the absence of soft anions which symbiotically motivate Ni^II to act as a soft acceptor. It thus does not react with H₂L² in the presence of hard ions such as Cl^–, Br^- and ClO ₄ ^– , but, the in situ reaction of the constituents produced the tetrahedral Ni^II complex, contrary to earlier reports of similar types of octahedral species.     

Interaction of 3H+ (as HTO) and 36Cl− (as Na36Cl) with crushed granite and corresponding fracture infill material investigated in column experiments

The transport of ³H⁺ (as HTO) and ³⁶Cl^? (as Na³⁶Cl) was investigated in the dynamic system, i.e., in the columns filled with crushed pure granite and fracture infill of various grain sizes. The aim of column experiments was to determine important transport parameter, such as the retardation, respectively distribution coefficients, Peclet numbers and hydrodynamic dispersion coefficients. Furthermore, the research was focused to quantification of the effect of grain size on migration of studied radionuclides. The experimental breakthrough curves were fitted by a model based on the erfc-function, assuming a linear reversible equilibrium sorption/desorption isotherm, and the above mentioned transport parameters were determined. The results showed that influence of grain size on sorption of ³H⁺ and ³⁶Cl^? was negligible. Retardation and distribution coefficients of both tracers converged to one and zero, respectively, in case of all fractions of crushed granite and infill material. Generally, the presumed ion exclusion of ³⁶Cl in anionic form was proved under given conditions, only very weak one seems to exist in a case of infill material. In principal, both radionuclides behaved as non-sorbing, conservative tracers. On the other hand, the influence of grain size on Peclet numbers value and on dispersion coefficient was observed for both crystalline materials, namely in agreement with theoretical suppositions that the values of Peclet numbers decrease with increasing grain size and values of dispersion coefficient increase.