Structure of 7-methyl-1(2)a,1(6)a,3(4)a-trihomocubane-1(6)a,3(4)a-dione,star-c12h12o2- a case of enantiomeric and rotational disorder

M r = 188.22, monoclinic, P21/n, a = 6.219 (2), b= 10.508 (2), c=7.339 (1)A, t= 107.64 (2) °, V= 457 ,/k 3, Z = 2, D m - - 1.360 (3), D x = 1.366 (2)Mgm -3, ~,(MoKa) = 0.7107/~, #= 0.053 mm -I, F(000) = 200, T= 293 K. Final R = 5.8% for 614 significant reflections. The molecule, which does not possess a centre of symmetry, occupies a crystallographic centre of symmetry because of the statistical enantiomeric and rotational disorder. Latticeenergy calculations, based on van der Waals attractive and repulsive potentials, clearly show minima at the observed disordered positions.

NMR relaxation study of disorder in the mixed system BP x GPI(1-x) and the low temperature transition from classical to quantum rotation

1H NMR spin-lattice relaxation time (T1) studies have been carried out in the temperature range 100 K to 4 K, at two Larmor frequencies 11.4 and 23.3 MHz, in the mixed system of betaine phosphate and glycine phosphite (BPxGPI(1-x)), to study the effects of disorder on the proton group dynamics. Analysis of T1 data indicates the presence of a number of inequivalent methyl groups and a gradual transition from classical reorientations to quantum tunneling rotations. At lower temperatures, microstructural disorder in the local environments of the methyl groups, result in a distribution in the activation energy (Ea) and the torsional energy gap (E01). For certain values of x, the magnetisation recovery shows biexponential behaviour at lower temperatures.

The effect of rapid solidification on the order-disorder transformation in iron-based alloys

The effect of rapid solidification on the ordering reaction in Fe---Si and Fe---Al alloys has been reported. It is shown that rapid solidification can influence the ordering reaction in alloys with higher critical ordering temperatures. For ordering reactions at lower temperatures, the effect is similar to that of solid-state quenching. Different factors influencing the ordering reactions and domain structures during rapid solidification of iron-based alloys are discussed.

Nature of ``Disorder'' in the Ordered Double Perovskite Sr2FeMoO6

The degree of B/B alternate cation order is known to heavily influence the magnetic properties of A2BB O6 double perovskites although the nature of such disorder has never been critically studied. Our detailed x-ray absorption fine structure studies in conjunction with synchrotron radiation x-ray diffraction experiments on polycrystalline Sr2FeMoO6 samples with various degrees of disorder reveal that a very high degree of short range order is preserved even in samples with highly reduced long range chemical order. Based on these experimental results and with the help of detailed structural simulations, we are able to model the nature of the disorder in this important class of materials and discuss the consequent implications on its physical properties.

Structural studies of analgesics and their interactions. VII. Stereoisomerism and disorder in the structure of oxyphenbutazone monohydrate

Oxyphenbutazone, C19H20N203, a metabolite and perhaps the active form of phenylbutazone, is a widely used non-narcotic analgesic and anti-inflammatory pyrazolidinedione derivative. The monohydrate of the compound crystallizes in the triclinic space group Pi with two molecules in a unit cell of dimensions a -- 9.491 (4), b = 10.261 (5), c = 11.036 (3)A and ¢~ = 72.2 (1), fl = 64.3 (1), 7 = 73.0 (1) °. The structure was solved by direct methods and refined to an R value of 0.107 for 1498 observed reflections. The butyl group in the molecule is disordered. The hydroxyl group occupies two sites with unequal occupancies. On account of the asymmetry at the two N atoms and one of the C atoms in the central five-membered ring, the molecule can exist in eight isomeric states, of which four are sterically unfavourable. The disorder in the position of the hydroxyl group can be readily explained on the basis of the existence, with unequal abundances, of all four sterically favourable isomers.The bond lengths and angles in the molecule are similar to those in phenylbutazone. The crystal structure is stabilized by van der Waals interactions, and O-H... O hydrogen bonds involving the carbonyl and the hydroxyl groups as well as a water molecule.

Structural Studies of Analgesics and Their Interactions. VIII.* Rotational Isomerism and Disorder in the Crystal Structure of Meelofenamie Acid

Meclofenamic acid, C I4HIICI2NO2, probably the most potent among analgesic fenamates, crystallizes in the triclinic space group P1, with a = 8.569 (5), b = 8.954(8), c -- 9.371 (4) A, ct = 103.0 (2), fl -- 103.5 (2), y = 92.4 (2) ° , Z = 2, D m = 1.43 (4), D c = 1.41 Mg m -3. The structure was solved by direct methods and refined to R = 0.135 for 1062 observed reflections. The anthranilic acid moiety in the molecule is nearly planar and is nearly perpendicular to the 2,6-dichloro-3-methylphenyl group. The molecules, which exist as hydrogen-bonded dimers, have an internal hydrogen bond involving the imino and the carboxyl groups. The methyl group is disordered and occupies two positions with unequal occupancies. The disorder can be satisfactorily explained in terms of the rotational isomerism of the 2,6-dichloro-3-methylphenyl group about the bond which connects it to the anthranilic acid moiety and the observed occupancies on the basis of packing considerations.

Disorder Induced Concomitant Polymorphism in 3-Fluoro-N-(3-fluorophenyl)benzamide

The occurrence of concomitant polymorphism in 3-fluoro-N-(3-fluorophenyl) benzamide has been identified to be due to the disorder in the crystal structure. Of the two modifications, the plate form (Form I) crystallizes in the monoclinic centrosymmetric space group C2/c with Z = 4, and the needle form (Form II) crystallizes in the noncentrosymmetric space group P21 with Z = 2. An interesting positional disorder at the bridging atoms in both forms holds the molecular conformation identical, while subtle variations brought by N−H···O hydrogen bonds along with weak C−H···F and F···F interactions result in packing polymorphism.

Critical test for Altshuler-Aronov theory: Evolution of the density of states singularity in double perovskite Sr2FeMoO6 with controlled disorder

With high-resolution photoemission spectroscopy measurements, the density of states (DOS) near the Fermi level (E-F) of double perovskite Sr2FeMoO6 having different degrees of Fe/Mo antisite disorder has been investigated with varying temperature. The DOS near E-F showed a systematic depletion with increasing degree of disorder, and recovered with increasing temperature. Altshuler-Aronov (AA) theory of disordered metals well explains the dependences of the experimental results. Scaling analysis of the spectra provides experimental indication for the functional form of the AA DOS singularity.

Optimal sleep-wake scheduling for quickest intrusion detection using sensor networks

We consider the problem of quickest detection of an intrusion using a sensor network, keeping only a minimal number of sensors active. By using a minimal number of sensor devices, we ensure that the energy expenditure for sensing, computation and communication is minimized (and the lifetime of the network is maximized). We model the intrusion detection (or change detection) problem as a Markov decision process (MDP). Based on the theory of MDP, we develop the following closed loop sleep/wake scheduling algorithms: (1) optimal control of Mk+1, the number of sensors in the wake state in time slot k + 1, (2) optimal control of qk+1, the probability of a sensor in the wake state in time slot k + 1, and an open loop sleep/wake scheduling algorithm which (3) computes q, the optimal probability of a sensor in the wake state (which does not vary with time), based on the sensor observations obtained until time slot k. Our results show that an optimum closed loop control on Mk+1 significantly decreases the cost compared to keeping any number of sensors active all the time. Also, among the three algorithms described, we observe that the total cost is minimum for the optimum control on Mk+1 and is maximum for the optimum open loop control on q.

Correlation of structural disorder with the reversible discharge capacity of nickel hydroxide electrode

Hydrothermal treatment of a slurry of badly crystalline (beta(bc)) nickel hydroxide at different temperatures (65-170 degrees C) results in the progressive ordering of the structure by the step-wise elimination of disorders. Interstratification is eliminated at 140 degrees C, while cation vacancies are eliminated at 170 degrees C. A small percentage of stacking faults continue to persist even in `crystalline' samples. Electrochemical investigations show that the crystalline nickel hydroxide has a very low (0.4 e/Ni) reversible charge storage capacity. An incidence of at least 15% stacking faults combined with cation vacancies is essential for nickel hydroxide to perform close to its theoretical (1 e/ Ni) discharge capacity. (c) 2005 The Electrochemical Society.

Effect of disorder on the exponent in the coherence region in high temperature superconductors

Effect of disorder on the electrical resistance near the superconducting transition temperature in the paracoherence region of high temperature YBa2CU3O7-delta (YBCO) thin film superconductor is reported. For this, c-axis oriented YBa2Cu3O7-delta thin films having superconducting transition width varying between 0.27 K and 6 K were deposited using laser ablation and high pressure oxygen sputtering techniques. Disorder in these films was further created by using 100 MeV oxygen and 200 MeV silver ions with varying fluences. It is observed that the critical exponent in the paracoherence region for films with high transition temperature and small transition width is in agreement with the theoretically predicted value (gamma = 1.33) and is not affected by disorder, while for films with lower transition temperature and larger transition width the value of exponent is much larger as compared to that theoretically predicted and it varies from sample to sample and usually changes with disorder induced by radiation. This difference in the behaviour of the exponent has been explained on the basis of differences in the strength of weak links and the transition between temperatures T. and T, is interpreted as a percolation like transition with disorder. (c) 2006 Elsevier B.V. All rights reserved.

NMR relaxation study of disorder in condensed matter: solid solutions of betaine phosphate and phosphite

Proton NMR relaxation measurements have been carried out in anti-ferroelectric Betaine phosphate (BP), ferroelectric Betaine phosphite (BPI) and the mixed system BPI(1-x)BPx, at 11.4MHz and 23.3MHz from 300K to 80K for x=0.0, 0.25, 0.45, 0.85, and 1.0. The temperature dependence of spin lattice relaxation time T, exhibits two minima as expected from the BPP model in BP and BPI. The Larmor frequency dependence of T, in the mixed system is rather unusual and exhibits different slopes for the low temperature wings at the two frequencies, which is a clear experimental evidence of the presence of different methyl groups with different activation energies (E-a) indicating disorder.

Optimal Sleep-Wake Policies for an Energy Harvesting Sensor Node

We study a sensor node with an energy harvesting source. In any slot,the sensor node is in one of two modes: Wake or Sleep. The generated energy is stored in a buffer. The sensor node senses a random field and generates a packet when it is awake. These packets are stored in a queue and transmitted in the wake mode using the energy available in the energy buffer. We obtain energy management policies which minimize a linear combination of the mean queue length and the mean data loss rate. Then, we obtain two easily implementable suboptimal policies and compare their performance to that of the optimal policy. Next, we extend the Throughput Optimal policy developed in our previous work to sensors with two modes. Via this policy, we can increase the through put substantially and stabilize the data queue by allowing the node to sleep in some slots and to drop some generated packets. This policy requires minimal statistical knowledge of the system. We also modify this policy to decrease the switching costs.

Disorder-driven electronic localization and phase separation in superconducting Fe1+yTe0.5Se0.5 single crystals

We have investigated the influence of Fe excess on the electrical transport and magnetism of Fe1+yTe0.5Se0.5 (y=0.04 and 0.09) single crystals. Both compositions exhibit resistively determined superconducting transitions (T-c) with an onset temperature of about 15 K. From the width of the superconducting transition and the magnitude of the lower critical field H-c1, it is inferred that excess of Fe suppresses superconductivity. The linear and nonlinear responses of the ac susceptibility show that the superconducting state for these compositions is inhomogeneous. A possible origin of this phase separation is a magnetic coupling between Fe excess occupying interstitial sites in the chalcogen planes and those in the Fe-square lattice. The temperature derivative of the resistivity d(rho)/d(T) in the temperature range T-c < T < T-a with T-a being the temperature of a magnetic anomaly, changes from positive to negative with increasing Fe. A log 1/T divergence of the resistivity above T-c in the sample with higher amount of Fe suggests a disorder-driven electronic localization.

Probing disorder in cubic pyrochlore Bi-1 Zn-5(1) Nb-0(1) O-5(7) (BZN) thin films

The dielectric response of pulsed laser ablated Bi-1 Zn-5(1) Nb-0(1) O-5(7) (BZN) thin films are investigated within the temperature range of 300-660 K and frequency range of 100 Hz-100 kHz Thin film exhibited a strong dielectric relaxation behavior A sharp rise in dielectric constant of BZN thin film at high temperatures is related to disorder in canon and anion lattices Observed dielectric relaxation implies a redistribution of charges within the unit cell This phenomenon suggests that the large change in dielectric constant is due to a dynamical rise of dipolar fluctuations in the unit cell XPS spectra of BZN (A(2)B(2)O(6)O') cubic pyrochlore confirm that the relaxation corresponds to the ionic hopping among the A and O' positions of several local potential minima Barrier height for hopping is distributed between 0 and 0 94 eV The O is spectrum confirms presence of two types of oxygen in BZN thin film The disorder in charge neutralized thin film is correlated with XPS spectra (C) 2010 Elsevier Ltd All rights reserved