Threshold electrical switching in As45Te55-xInx and As50Te50-xInx glasses

The electrical switching behaviour of As₄₅Te_55-xIn_x (5≤x≤15) and As₅₀Te_50-xIn_x (2.5≤x≤11.5) has been studied over a wide range of compositions. These glasses are found to exhibit threshold switching. The composition dependence of switching voltage (V_t) has been found to exhibit a change in slope and a local minimum at compositions x=10 and 12.5 for As₄₅Te_55-xIn_x and x=7.5 and 10.8 for As₅₀Te_50-xIn_x, respectively. The slope change in V_t verses x and the local minimum have been identified using two network topological effects, namely the rigidity percolation threshold and the chemical threshold. Received: 23 August 2001 / Accepted: 27 August 2001 / Published online: 11 February 2002     

Electronic structure of CeAl2 thin films studied by X-ray absorption spectroscopy

We report X-ray absorption near edge structures (XANES) study of CeAl₂ thin films of various thicknesses, 40-120 nm, at Al K- and Ce L₃-edges. The threshold of the absorption features at the Al K-edge shifts to the higher photon energy side as film thickness decreases, implying a decreased in Al p-orbital charges. On the other hand, from Ce L₃-edge spectra, we observed a decrease in the 5d4f occupancy as the surface-to-bulk ratio increases. The valence of Ce in these thin films, as revealed by the Ce L₃-edge spectral results, is mainly trivalent. From a more detailed analysis we found a small amount of Ce⁴⁺ contribution, which increases with decreasing film thickness. Our results indicate that the surface-to-bulk ratio is the key factor which affects the electronic structure of CeAl₂ thin films. The above observations also suggest that charge transfer from Al to Ce is associated with the decrease of the film thickness.     

Influence of the distal his in imparting imidazolate character to the proximal his in heme peroxidase: (1)h NMR spectroscopic study of cyanide-inhibited his42-->ala horseradish peroxidase

The functional higher oxidation states of heme peroxidases have been proposed to be stabilized by the significant imidazolate character of the proximal His. This is induced by a "push-pull" combination effect produced by the proximal Asp that abstracts ("pulls") the axial His ring N(delta)H, along with the distal protonated His that contributes ("pushes") a strong hydrogen bond to the distal ligand. The molecular and electronic structure of the distal His mutant of cyanide-inhibited horseradish peroxidase, H42A-HRPCN, has been investigated by NMR. This complex is a valid model for the active site hydrogen-bonding network of HRP compound II. The (1)H and (15)N NMR spectral parameters characterize the relative roles of the distal His42 and proximal Asp247 in imparting imidazolate character to the axial His. 1D/2D spectra reveal a heme pocket molecular structure that is highly conserved in the mutant, except for residues in the immediate proximity of the mutation. This conserved structure, together with the observed dipolar shifts of numerous active site residue protons, allowed a quantitative determination of the orientation and anisotropies of the paramagnetic susceptibility tensor, both of which are only minimally perturbed relative to wild-type HRPCN. The quantitated dipolar shifts allowed the factoring of the hyperfine shifts to reveal that the significant changes in hyperfine shifts for the axial His and ligated (15)N-cyanide result primarily from changes in contact shifts that reflect an approximately one-third reduction in the axial His imidazolate character upon abolishing the distal hydrogen-bond to the ligated cyanide. Significant changes in side chain orientation were found for the distal Arg38, whose terminus reorients to partially fill the void left by the substituted His42 side chain. It is concluded that 1D/2D NMR can quantitate both molecular and electronic structural changes in cyanide-inhibited heme peroxidase and that, while both residues contribute, the proximal Asp247 is more important than the distal His42 in imparting imidazole character to the axial His 170.     

Effect of 60Co γ-irradiation on structural and optical properties of thin films of Ga10Se80Hg10

Thin films of Ga₁₀Se₈₀Hg₁₀ have been deposited onto a chemically cleaned Al₂O₃ substrates by thermal evaporation technique under vacuum. The investigated thin films are irradiated by ⁶⁰Co γ-rays in the dose range of 50–150 kGy. X-ray diffraction patterns of the investigated thin films confirm the preferred crystallite growth occurs in the tetragonal phase structure. It also shows, the average crystallite size increases after γ-exposure, which indicates the crystallinity of the material increases after γ-irradiation. These results were further supported by surface morphological analysis carried out by scanning electron microscope and atomic force microscope which also shows the crystallinity of the material increases with increasing the γ-irradiation dose. The optical transmission spectra of the thin films at normal incidence were investigated in the spectral range from 190 to 1100 nm. Using the transmission spectra, the optical constants like refractive index (n) and extinction coefficient (k) were calculated based on Swanepoel’s method. The optical band gap (E_g) was also estimated using Tauc’s extrapolation procedure. The optical analysis shows: the value of optical band gap of investigated thin films decreases and the corresponding absorption coefficient increases continuously with increasing dose of γ-irradiation.     

Highly facile and stereoselective intramolecular [2 +2]photocycloadditions of bis(alkenoyl)ketenedithioacetals

The conformational change induced by the introduction of a ketenedithioacetal moiety at C-4 of 1,7-substituted-1,6-heptadiene-3,5-diones results in favorable spatial relationships between the alkenoyl groups to effect efficient intramolecular cycloadditions: irradiation of bis(alkenoyl)ketenedithioacetals in solution leads to facile and stereospecific intramolecular [2 + 2] photocycloadditions resulting in the formation of substituted bicyclo[3.2.0]heptane-2,4-diones, the observed conformational rigidity of which is attributed to the push-pull character of the ketenedithioacetal group.     

Electrical switching studies on As<Subscript>40</Subscript>Te<Subscript>60-x</Subscript>Se<Subscript>x</Subscript> and As<Subscript>35</Subscript>Te<Subscript>65-x</Subscript>Se<Subscript>x</Subscript> glasses

The I–V characteristics of bulk As₄₀Te_60-xSe_x and As₃₅Te_65-xSe_x glasses have been studied with a current sweep of 0–18 mA-0, over a wide range of compositions (4≤x≤22). All the glasses studied showed a threshold electrical switching behaviour. The number of switching cycles withstood by the samples has been found to depend on the ON-state current. It is seen that the switching voltages increase with increase in selenium content. Further, the switching voltages are found to be almost independent of the thickness of the sample (d), in the range 0.18–0.3 mm. Also, the switching voltages and the number of switching cycles withstood by the samples are found to decrease with temperature. Received: 6 November 2002 / Accepted: 8 November 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. Fax: +91-80/360-0135, E-mail: sasokan@isu.iisc.ernet.in     

Direct Similarity Analysis of Generalized Burgers Equations and Perturbation Solutions of Euler–Painlevé Transcendents

Similarity reductions of the generalized Burgers equation     , where α, β, and γ are non-negative constants, n a positive integer and   j = 0, 1, 2  , are obtained by the direct method of Clarkson and Kruskal [ 1 ]. This is the first work to report the similarity variables as an incomplete gamma function and also as a power of     , and to provide a perturbation solution of an Euler–Painlevé transcedent.     

Electrical transport and high pressure studies on bulk Ge20Te80 glass

The electrical resistivity of bulk Ge₂₀Te₈₀ has been measured as a function of pressure and temperature. At 5 GPa, an amorphous semiconductor-to-crystalline metal transition has been observed. The sample recovered from the high pressure cell, after the application of 7 GPa, has a face-centred cubic structure with a lattice constant of 6·42 A. In crystalline sample, the semiconductor-to-metal transition occurs at 7 GPa. The thermoelectric power has also been measured for glassy samples in the temperature range 300–240 K.