Study of electron states of solids by techniques of electron spectroscopy

Studies of valence bands and core levels of solids by photoelectron spectroscopy are described at length. Satellite phenomena in the core level spectra have been discussed in some detail and it has been pointed out that the intensity of satellites appearing next to metal and ligand core levels critically depends on the metal-ligand overlap. Use of photoelectron spectroscopy in investigating metal-insulator transitions and spin-state transitions in solids is examined. It is shown that relative intensities of metal Auger lines in transition metal oxides and other systems provide valuable information on the valence bands. Occurrence of interatomic Auger transitions in competition with intraatomic transitions is discussed. Applications of electron energy loss spectroscopy and other techniques of electron spectroscopy in the study of gas-solid interactions are briefly presented.

Stability of Fe3+ -VO defect pairs in polycrystalline Pb(Ti,Zr)O3

The intensity of the EPR signal with g = 5.985 arising from a ferric ion â oxygen vacancy defect pair (Fe3+ â VO) in PbTiO3, varies with the extent of PbO nonstoichiometry at constant Fe3+ content due to an increased oxygen vacancy concentration. In PZT solid solutions, the signal intensity decreases with an increase in Zr. A lower intensity is also noticed for Fe3+ â VO signals in PbZrO3. This behaviour is explained on the basis of PbO nonstoichiometry arising from independent Pb- and O-vacancies as well as the randomly distributed crystallographic shear (CS) plane defects. The contribution to PbO nonstoichiometry from CS planes is larger in high zirconium compositions of PZT.

Light scattering studies on solutions of chlorinated rubber

Measurements have been made of the depolarisation factors \sigma u ,\sigma v ,\sigma h, and the intensity of scattering in the horizontal transverse direction, in the case of solutions of four different samples of chlorinated rubber in carbon tetrachloride. The size, shape and molecular weight of the micelles have been deduced by the application of the light scattering theories of Gans, Vrklajan and Katalinic and Debye. The extent to which the degradation of the rubber molecule occurs on chlorination has also been assessed.

Modeling the role of competition and cooperation in the evolution of katydid acoustic synchrony

The precise timing of individual signals in response to those of signaling neighbors is seen in many animal species. Synchrony is the most striking of the resultant timing patterns. One of the best examples of acoustic synchrony is in katydid choruses where males produce chirps with a high degree of temporal overlap. Cooperative hypotheses that speculate on the evolutionary origins of acousti synchrony include the preservation of the species-specific call pattern, reduced predation risks, and increased call intensity. An alternative suggestion is that synchrony evolved as an epiphenomenon of competition between males in response to a female preference for chirps that lead other chirps. Previous models investigating the evolutionary origins of synchrony focused only on intrasexual competitive interactions. We investigated both competitive and cooperative hypotheses for the evolution of synchrony in the katydid Mecopoda ``Chirper'' using physiologically and ecologically realistic simulation models incorporating the natural variation in call features, ecology, female preferences, and spacing patterns, specifically aggregation. We found that although a female preference for leading chirps enables synchronous males to have some selective advantage, it is the female preference for the increased intensity of aggregations of synchronous males that enables synchrony to evolve as an evolutionarily stable strategy.

Raman Spectroscopic study of valinomycin-metal complexes

Valinomycin, an ionophore of considerable interest for its ion selectivity, and its K+, Mg2+, Ba2+, and Ca2+ complexes were studied by Raman spectroscopy. Each complex has a characteristic spectrum which differs from that of uncomplexed valinomycin, suggesting several distinct structures for each of the metal-valinomycin complexes. The biologically active potassium complex shows the most significant changes in its spectrum, especially in the intensity of the symmetric C---H stretching vibration of CH3 and the convergence of the two ester carbonyl stretching vibration bands into one complex formation. These results are due to the unique orientation of the ester carbonyl groups toward the caged potassium ion and the resulting more free rotation of isopropyl side chains. The divalent cation-valinomycin complexes examined showed spectra which differed in each case uniquely from both valinomycin and its complex with potassium.

ESR studies of non-silicate inorganic glasses through their glass transformation ranges

ESR spectra of three inorganic glasses doped with Mn2+ and Fe3+ have been studied through their glass transition temperatures (Tg). Spectral features in each case have been discussed with reference to site symmetries. The intensity of the ESR signal has been bound to decrease in the region of Tg. An attempt has been made to explain this interesting feature on the basis of a two-state model.

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.

Temperature dependence of the surface conductivity of YBa2Cu3O7−δ accompanying the change in the concentration of dimerized oxygen holes

The intensity of inelastically scattered electrons measured by electron energy loss spectroscopy has been employed to monitor the surface conductivity of YBa2Cu3O6.9 as a function of temperature. The study shows a drastic change in surface conductivity precedes the superconducting transition at 90K. The increase in surface conductivity is accompanied by the formation of dimerized holes in the oxygen derived p-band. This phenomenon is not observed in the non-superconducting YBa2Cu3O6.2.

Metal Auger intensity ratios as a probe for change-transfer effects in aluminum-covered transition metal

Marked changes in the LVV/LMV and LVV/LMM Auger intensity ratios of Co, Ni and Cu are observed on depositing Al on their surfaces. These changes, ascribed to charge-transfer or hybridization effects, are accompanied by changes in the intensity of the satellites next to the core levels of the transition metals.

Optical and nonlinear absorption properties of Na doped ZnO nanoparticle dispersions

We report linear and nonlinear optical properties of the biologically important Na doped ZnO nanoparticle dispersions. Interesting morphological changes involving a spherical to flowerlike transition have been observed with Na doping. Optical absorption measurements show an exciton absorption around 368 nm. Photoluminescence measurements reveal exciton recombination emission, along with shallow and deep trap emissions. The increased intensity of shallow trap emission with Na doping is attributed to oxygen deficiency and shape changes associated with doping. Nonlinear optical measurements show a predominantly two-photon induced, excited state absorption, when excited with 532 nm, 5 ns laser pulses, indicating potential optical limiting applications.

Measurement of sensitivities for the thermal recording of laser beams

A simple technique for determining the energy sensitivities for the thermographic recording of laser beams is described. The principle behind this technique is that, if a laser beam with a known spatial distribution such as a Gaussian profile is used for imaging, the radius of the thermal image formed depends uniquely on the intensity of the impinging beam. Thus by measuring the radii of the images produced for different incident beam intensities the minimum intensity necessary (that is, the threshold) for thermographic imaging is found. The diameter of the laser beam can also be found from this measurement. A simple analysis based on the temperature distribution in the laser heated material shows that there is an inverse square root dependence on pulse duration or period of exposure for the energy fluence of the laser beam required, both for the threshold and the subsequent increase in the size of the recording. It has also been shown that except for low intensity, long duration exposure on very low conductivity materials, heat losses are not very significant.

Incomplete decomposition of alkali metal azides

The thermal decomposition of sodium azide has been studied in the temperature range 240–360°C in vacuum and under pressure of an inert gas, argon. The results show that the decomposition is partial 360°C. From the observations made in the present work, namely: (i) the decomposition is incomplete both under vacuum and inert gas; (ii) mass spectrometric studies do not reveal any decrease in the intensity of the background species, CO+2, CO+, H2O+, and (iii) sodium metal remains in the ‘free state’ as seen by the formation of a metallic mirror at temperatures above 300°C, it has been argued that the partial nature of decompostion is due to the confinement of the decomposition to intermosaic regions within the lattice.

Effect of temperature, pressure and additives on pyrolysis of polystyrene peroxide

Some aspects of the pyrolysis of polystyrene peroxide (PSP) have been examined. Low-temperature decomposition studies at 60°C and 70°C have been carried out to elucidate the ageing behaviour of PSP. The exothermic decomposition was found to be complete in 44 h at 70°C suggesting that all peroxide bonds have broken. Enthalpy measurements of the aged samples were carried out as a function of storage time. Ageing was also followed by infrared spectroscopy, and the intensity of the peroxide absorption around 1050 cm−1 was found to decrease with ageing time. Benzaldehyde formed as a result of PSP pyrolysis is readily converted into benzoic acid, which crystallizes during the ageing process. Pyrolysis—gas chromatographic studies have shown that up to 450°C the basic decomposition mechanism (i.e., the formation of benzaldehyde and formaldehyde as the major products) does not change. No effect of pressure on the decomposition exotherm in differential thermal analysis was observed, suggesting that peroxide composition involves only condensed phase reactions. Hydroquinone, p-aminophenol and cadmium sulphide were found to retard the thermal decomposition of PSP, suggesting that these compounds would be potential antioxidants for polymers.

Approximation of the perturbation equations of a quasi-linear hyperbolic system in the neighborhood of a bicharacteristic

In 1956 Whitham gave a nonlinear theory for computing the intensity of an acoustic pulse of an arbitrary shape. The theory has been used very successfully in computing the intensity of the sonic bang produced by a supersonic plane. [4.] derived an approximate quasi-linear equation for the propagation of a short wave in a compressible medium. These two methods are essentially nonlinear approximations of the perturbation equations of the system of gas-dynamic equations in the neighborhood of a bicharacteristic curve (or rays) for weak unsteady disturbances superimposed on a given steady solution. In this paper we have derived an approximate quasi-linear equation which is an approximation of perturbation equations in the neighborhood of a bicharacteristic curve for a weak pulse governed by a general system of first order quasi-linear partial differential equations in m + 1 independent variables (t, x1,…, xm) and derived Gubkin's result as a particular case when the system of equations consists of the equations of an unsteady motion of a compressible gas. We have also discussed the form of the approximate equation describing the waves propagating upsteam in an arbitrary multidimensional transonic flow.

Chemical modification studies on Abrus agglutinin Involvement of tryptophan residues in sugar binding

The galactose-binding lectin from the seeds of the jequirity plant (Abrus precatorius) was subjected to various chemical modifications in order to detect the amino acid residues involved in its binding activity. Modification of lysine, tyrosine, arginine, histidine, glutamic acid and aspartic acid residues did not affect the carbohydratebinding activity of the agglutinin. However, modification of tryptophan residues carried out in native and denaturing conditions with N-bromosuccinimide and 2- hydroxy-5-nitrobenzyl bromide led to a complete loss of its carbohydrate-binding activity. Under denaturing conditions 30 tryptophan residues/molecule were modified by both reagents, whereas only 16 and 18 residues/molecule were available for modification by N-bromosuccinimide and 2-hydroxy-5-nitrobenzyl bromide respectively under native conditions. The relative loss in haemagglutinating activity after the modification of tryptophan residues indicates that two residues/molecule are required for the carbohydrate-binding activity of the agglutinin. A partial protection was observed in the presence of saturating concentrations of lactose (0.15 M). The decrease in fluorescence intensity of Abrus agglutinin on modification of tryptophan residues is linear in the absence of lactose and shows a biphasic pattern in the presence of lactose, indicating that tryptophan residues go from a similar to a different molecular environment on saccharide binding. The secondary structure of the protein remains practically unchanged upon modification of tryptophan residues, as indicated by c.d. and immunodiffusion studies, confirming that the loss in activity is due to modification only.