ESR study of exchange coupled pairs in copper diethyldithiocarbamate—explanation of the low temperature hyperfine anomaly

A study of the hyperfine interaction in the ESR of Cu-Cu pairs in single crystals of copper diethyldithiocarbamate as a function of temperature has shown distinct differences in the hyperfine structure in the two fine structure transitions at 20 K, the spectrum not having the same hyperfine intensity pattern in the low field fine structure transition in contrast to that of the high field transition. The details of the structure of both the fine structure transitions in the 20 K spectrum have now been explained by recognizing the fact that the mixing of the nuclear spin states caused by the anisotropic hyperfine interaction affects the electron spin states | + 1 > and | −> differently. This has incidentally led to a determination of the sign ofD confirming the earlier model. The anomalous hyperfine structure is found to become symmetric at 77 K and 300 K. It is proposed that the reason for this lies in the dynamics of spin-lattice interaction which limits the lifetime of the spin states in each of the electronic levels | − 1 >, | 0 > and | + 1 > The estimate of spin-lattice relaxation time agrees with those indicated from other studies. The model proposed here for the hyperfine interaction of pairs in the electronic triplet state is of general validity.

Effect of manganese dioxide on the thermal decomposition of ammonium perchlorate

Thermal decomposition of powdered ammonium perchlorate, catalysed by manganese dioxide (MnO2), has been studied in the low concentration ranges of the catalyst. MnO2 sensitises the thermal decomposition of ammonium perchlorate. The activation energy estimations of catalysed ammonium perchlorate show that the value is about 30 kcal/mol throughout the low and the high temperature regions whereas uncatalysed ammonium perchlorate gives two activation energies, 20 kcal/mol in the low temperature region (280-320°C) and 60 kcal/mol in the higher temperature region (350-390°C). This behaviour has been explained on the basis of an electron transfer process. The effectiveness of MnO2 in the thermal decomposition further increases on pre-heating the sample at 50°C for two weeks; manganese ions enter the ammonium perchlorate lattice during the process of pre-heating.

Anderson transitions in Ln1-xSrxCoO3 (Ln=Pr or Nd)

Electrical conductivity measurements show that Ln1-xSrxCoO3, (Ln = Pr or Nd) undergoes a non-metal-metal transition when x-0 3. The d.c. conductivity of compositions with 0lattice of Co3+, form a degenerate gas and that the states at the Fermi energy are Anderson localized.

Phase diagram of vortex matter in layered superconductors with tilted columnar pinning centers

We study the vortex matter phase diagram of a layered superconductor in the presence of columnar pinning defects, tilted with respect to the normal to the layers. We use numerical minimization of the free energy written as a functional of the time-averaged vortex density of the Ramakrishnan-Yussouff form, supplemented by the appropriate pinning potential. We study the case where the pin density is smaller than the areal vortex density. At lower pin concentrations, we find, for temperatures of the order of the melting temperature of the unpinned lattice, a Bose glass type phase which at lower temperatures converts, via a first-order transition, to a Bragg glass, while, at higher temperatures, it crosses over to an interstitial liquid. At somewhat higher concentrations, no transition to a Bragg glass is found even at the lowest temperatures studied. While qualitatively the behavior we find is similar to that obtained using the same procedures for columnar pins normal to the layers, there are important and observable quantitative differences, which we discuss.

Entanglement production due to quench dynamics of an anisotropic XY chain in a transverse field

We compute concurrence and negativity as measures of two-spin entanglement generated by a power-law quench (characterized by a rate tau(-1) and an exponent alpha) which takes an anisotropic XY chain in a transverse field through a quantum critical point (QCP). We show that only spins separated by an even number of lattice spacings get entangled in such a process. Moreover, there is a critical rate of quench, tau(-1)(c), above which no two-spin entanglement is generated; the entire entanglement is multipartite. The ratio of the entanglements between consecutive even neighbors can be tuned by changing the quench rate. We also show that for large tau, the concurrence (negativity) scales as root alpha/tau(alpha/tau), and we relate this scaling behavior to defect production by the quench through a QCP.

Evolution of Grain-Boundary Microstructure and Texture in Interstitial-Free Steel Processed by Equal-Channel Angular Extrusion

The equal-channel angular extrusion (ECAE) of Ti-bearing interstitial-free (IF) steel was performed following two different routes, up to four passes, at a temperature of 300 degrees C. The ECAE led to a grain refinement to submicron size. After the second pass, the grain size attained saturation thereafter. The microstructural analysis indicated the presence of coincident-site lattice (CSL) boundaries in significant fraction, in addition to a high volume fraction of high-angle random boundaries and some low-angle boundaries after the deformation. Among the special boundaries, Sigma 3 and Sigma 13 were the most prominent ones and their fraction depended on the processing route followed. A deviation in the misorientation angle distribution from the Mackenzie distribution was noticed. The crystallographic texture after the first pass resembled that of simple shear, with the {112}, {110}, and {123} aligned to the macroscopic shear plane.

Stereospecific photodimerization of coumarins in crystalline inclusion complexes. Molecular and crystal structure of 1:2 complex of (S,S)-(-)-1,6-bis(o-chlorophenyl)-1,6-diphenyl-hexa-2,4-diyne-1,6-diol and coumarin

Proximity of molecules is a crucial factor in many solid- state photochemical processes.'S2 The biomolecular photodimerization reactions in the solid state depend on the relative geometry of reactant molecules in the crystal lattice with center-to-center distance of nearest neighbor double bonds of the order of ca. 4 A. This fact emanates from the incisive studies of Schmidt and Cohen.2 One of the two approaches to achieve this distance requirement is the so-called "Crystal-Engineering" of structures, which essentially involves the introduction of certain functional groups that display in-plane interstacking interactions (Cl...Cl, C-He-0, etc.) in the crystal The chloro group is by far the most successful in promoting the /3- packing m ~ d e ,th~o,u~gh recent studies have shown its limitations? Another approach involves the use of constrained media in which the reactants could hopefully be aligned.

Glass transitions in arsenic-selenium glasses

Glaiis transitions of As-Se glasses have been investigated over a wide range of compositions by using differential scanning calorimetry. The variation of Tg with composition has been interpreted on the basis of a bond-lattice model.

Spatial correlation in grain misorientation distribution

Grain misorientation was studied in relation to the nearest neighbor's mutual distance using electron back-scattered diffraction measurements. The misorientation correlation function was defined as the probability density for the occurrence of a certain misorientation between pairs of grains separated by a certain distance. Scale-invariant spatial correlation between neighbor grains was manifested by a power law dependence of the preferred misorientation vs. inter-granular distance in various materials after diverse strain paths. The obtained negative scaling exponents were in the range of -2 +/- 0.3 for high-angle grain boundaries. The exponent decreased in the presence of low-angle grain boundaries or dynamic recrystallization, indicating faster decay of correlations. The correlations vanished in annealed materials. The results were interpreted in terms of lattice incompatibility and continuity conditions at the interface between neighboring grains. Grain-size effects on texture development, as well as the implications of such spatial correlations on texture modeling, were discussed.

Diffusion and Creep in Silica-Doped Tetragonal Zirconia

Silica segregation at two grain junctions or in amorphous triple junction pockets can influence creep by altering the grain-boundary diffusion coefficient. Although the addition of silica to superplastic yttria-stabilized tetragonal zirconia enhances ductility, differences in reported creep parameters have limited critical identification of rate controlling mechanisms. The present study on a pure 3 mol% yttria-stabilized tetragonal zirconia (3YTZ) and 3YTZ with 0.39 or 3.9 wt% silica involved a detailed characterization of creep over a wide range of experimental conditions and also tracer diffusion measurements. The data broadly show transitions in creep stress exponents from n∼1 to ∼2 to ∼3 with a decrease in the stress. The data at high stresses are consistent with Coble diffusion creep, and creep at lower stresses is attributed to interface-controlled diffusion creep. Measurements indicated that silica does not have any significant influence on grain boundary or lattice diffusion, and this is consistent with the observation that 3YTZ and 3YTZ with 0.39% or 3.9% silica exhibit essentially identical creep behavior in the Coble creep regime. Silica influences the interface control process so that the transitions in stress exponents are pushed to lower stresses with an increase in silica content.

Tendency to promote ferroelectric distortion in Pr-modified PbTiO3

Structural, microstructural, and dielectric studies have been carried out on Pr-modified PbTiO3. A comparative analysis with La-modified PbTiO3 suggests that for chemical modification by same amount, the Pr-modified system has larger tetragonal strain and Curie point. No clear feature of relaxor ferroelectric state is observed for Pr concentration as high as x=0.35, suggesting that Pr modification is less effective, as compared to La-modification, in inducing a relaxor ferroelectric state. Results suggest that inspite of increased chemical disorder, Pr modification partly tends to restore the ferroelectric distortion of the lattice through partial occupancy of the Pr4+ ions on the Ti4+ sites.

Temperature dependent structural properties of nanocrystalline SnS structures

This letter explores the structural behavior of nanocrystalline tin mono sulfide (SnS) structures with respect to temperature (100-600 K). These studies emphasize that the structural properties of SnS nanocrystalline structures depend on the surrounding temperature. The lattice parameters of SnS nanocrystals slightly varied like their microstructures with the increase of temperature. These changes strongly influence the optical properties of SnS nanostructures. On the other hand, the structures exhibited higher strain (similar to 0.44%) than that of microstructured (0.3%) and bulk (0.12%) counterparts. The observed results are discussed under the light of existing concepts and reported.

Ce0.67Cr0.33O2.11: A New Low-Temperature O-2 Evolution Material and H-2 Generation Catalyst by Thermochemical Splitting of Water

Ce0.67Cr0.33O2.11 was synthesized by hydrothermal method using diethylenetriamine as complexing agent (Chem. Mater. 2008, 20, 7268). Ce0.67Cr0.33O2.11 being the only compound likes UO2+delta to have excess oxygen, it releases a large proportion of its lattice oxygen (0.167 M [O]/mole of compound) at relatively low temperature (465 degrees C) directly and it has been utilized for generation of H-2 by thermo-splitting of water. An almost stoichiometric amount of H-2 (0.152 M/Mole of compound) is generated at much lower temperature (65 degrees C). There is an almost comparable amount of oxygen release and hydrogen generation over this material at very low temperature comparedto other CeO2-MOx (Mn, Fe, Cu, and Ni) mixed-oxide solid solutions (O-2 evolution >= 1300 degrees C and H-2 generation at 1000 degrees C). The reversible nature of oxygen release and intake of this material is attributed to its fluorite Structure and coupling between the Ce4+/Ce3+ and Cr4+/6+/Cr3+ redox couples. Compound shows reversible oxygen release and intake by H2O absorption and subsequent hydrogen release to gain parent structure and hence this material can be utilized for generation of H-2 at very low temperature by thermo-chemical splitting of water.

Low-lying states of transverse substituted trans-polyacetylene and trans-polyacetylene: A comparative DMRG study

The density-matrix renormalization group (DMRG) method is used for a comparative study of low-lying excitations in trans-polyacetylene (t-PA) and transversely substituted t-PA (TS-t-PA). We have employed the Pariser-Parr-Pople model Hamiltonian which incorporates long-range electronic correlations to model these systems. We find some fundamental differences in the excited states of the t-PA and TS-t-PA. We find that the lowest two-photon allowed excited state in TS-t-PA is not made up of two triplet excitons and the gap to this state is nonzero even for undimerized chains in the thermodynamic limit. Contrary to earlier results for the Hubbard model, we find that the lowest two-photon state is always below the first optically allowed state in all the systems studied here making TS-t-PA systems only weakly fluorescent materials. Nonresonant tumbling averaged linear and third harmonic generation optic coefficients of TS-t-PA systems are also much smaller than that of t-PA.

2-[(E)-(4-hydroxy-3-methoxybenzylidene)amino]-N-(2-methylphenyl)-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxamide

The title compound, C24H24N2O3S, exhibits antifungal and antibacterial properties. The compound crystallizes with two molecules in the asymmetric unit, with one molecule exhibiting 'orientational disorder' in the crystal structure with respect to the cyclohexene ring. The o-toluidine groups in both molecules are noncoplanar with the respective cyclohexene-fused thiophene ring. In both molecules, there is an intramolecular N-H...N hydrogen bond forming a pseudo-six-membered ring which locks the molecular conformation and eliminates conformational flexibility. The crystal structure is stabilized by O-H...O hydrogen bonds; both molecules in the asymmetric unit form independent chains, each such chain consisting of alternating 'ordered' and 'disordered' molecules in the crystal lattice.