Interplay between proton ordering and ferroelectric polarization in H-bonded KDP-type crystals

The origin of ferroelectricity in KH2PO4 (KDP) is studied by first-principles electronic structure calculations. In the low-temperature phase, the collective off-centre ordering of the protons is accompanied by an electronic charge delocalization from the near and localization at the far oxygen within the O-H...O bonds. Electrostatic forces. then, push the K+ ions towards off-centre positions, and induce a macroscopic polarization. The analysis of the correlation between different geometrical and electronic quantities, in connection with experimental data. supports the idea that the role of tunnelling in isotopic effects is irrelevant. Instead, geometrical quantum effects appear to play a central role. (C) 2001 Elsevier Science B.V. All rights reserved.

Atomic ordering in nano-layered FePt: Multiscale Monte Carlo simulation

Nano- and meso-scale simulation of chemical ordering kinetics in nano-layered L1(0)-AB binary intermetallics was performed. In the nano- (atomistic) scale Monte Carlo (MC) technique with vacancy mechanism of atomic migration implemented with diverse models for the system energetics was used. The meso-scale microstructure evolution was, in turn, simulated by means of a MC procedure applied to a system built of meso-scale voxels ordered in particular L1(0) variants. The voxels were free to change the L1(0) variant and interacted with antiphase-boundary energies evaluated within the nano-scale simulations. The study addressed FePt thin layers considered as a material for ultra-high-density magnetic storage media and revealed metastability of the L1(0) c-variant superstructure with monoatomic planes parallel to the (001)-oriented layer surface and off-plane easy magnetization. The layers, originally perfectly ordered in the c-variant, showed discontinuous precipitation of a- and b-L1(0)-variant domains running in parallel with homogeneous disordering (i.e. generation of antisite defects). The domains nucleated heterogeneously on the free monoatomic Fe surface of the layer, grew inwards its volume and relaxed towards an equilibrium microstructure of the system. Two

Atomic ordering in nano-layered FePt

Monte Carlo simulation of chemical ordering kinetics in nano-layered L1₀ AB binary intermetallics was performed. The study addressed FePt thin layers considered as a material for ultra-high-density magnetic storage media and revealed metastability of the L1₀ c-variant superstructure with monoatomic planes parallel to the surface and off-plane easy magnetization. The layers, originally perfectly ordered in a c-variant of the L1₀ superstructure, showed homogeneous disordering running in parallel with a spontaneous re-orientation of the monoatomic planes leading to a mosaic microstructure composed of a- and b-L1₀-variant domains. The domains nucleated heterogeneously on the surface of the layer and grew discontinuously inwards its volume. Finally, the domains relaxed towards an equilibrium microstructure of the system. Two “atomistic-scale” processes: (i) homogeneous disordering and (ii) nucleation of the a- and b-L1₀-variant domains showed characteristic time scales. The same was observed for the domain microstructure relaxation. The discontinuous domain growth showed no definite driving force and proceeded due to thermal fluctuations. The above complex structural evolution has recently been observed experimentally in epitaxially deposited thin films of FePt.

Combining preference ordering and contingent valuation methods to assess non market benefit of alternative afforestation projects

The application of the contingent valuation method (CVM) in this paper incorporates a prior preference ordering of several alternative future afforestation programmes which could be implemented in Ireland over the next decade. This particular experimental design is thereby shown to reveal the potentially conflicting preferences of different groups within society. These findings are used to devise appropriate CVM scenarios to take account, not only of the efficiency gains of choosing a single policy alternative over others, but also the effects on the distribution of non market benefit between different groups within society, arising from choice between alternatives. (C) 1998 Elsevier Science Ltd. All rights reserved.

Ordering effects and choice set awareness in repeat-response stated preference studies

We present an experiment designed to investigate the presence and nature of ordering effects within repeat-response stated preference (SP) studies. Our experiment takes the form of a large sample, full-factorial, discrete choice SP exercise investigating preferences for tap water quality improvements. Our study simultaneously investigates a variety of different forms of position-dependent and precedent-dependent ordering effect in preferences for attributes and options and in response randomness. We also examine whether advanced disclosure of the choice tasks impacts on the probability of exhibiting ordering effects of those different types. We analyze our data both non-parametrically and parametrically and find robust evidence for ordering effects. We also find that the patterns of order effect in respondents' preferences are significantly changed but not eradicated by the advanced disclosure of choice tasks a finding that offers insights into the choice behaviors underpinning order effects. © 2011 Elsevier Inc.

Proton ordering energetics in ice phases

Results from first-principles calculations on the subtle energetics of proton ordering in ice phases are shown only to depend on the electrostatic components of the total energy. Proton ordered ice phases can therefore be predicted using electronic structure methods or a tailored potential model. However, analysis of the electron density reveals that high order multipole components, up to hexadecapole, are needed to adequately capture total energy differences between proton ordered and disordered phases. This suggests that current potential models may be unable to reproduce the position of proton ordered ice phases in the phase diagram without extensions to describe high order electrostatics. (c) 2006 Elsevier B.V. All rights reserved.

Ordering the cytochrome c-initiated caspase cascade:hierarchical activation of caspases-2, -3, -6, -7, -8, and -10 in a caspase-9-dependent manner

Exit of cytochrome c from mitochondria into the cytosol has been implicated as an important step in apoptosis. In the cytosol, cytochrome c binds to the CED-4 homologue, Apaf-1, thereby triggering Apaf-1-mediated activation of caspase-9. Caspase-9 is thought to propagate the death signal by triggering other caspase activation events, the details of which remain obscure. Here, we report that six additional caspases (caspases-2, -3, -6, -7, -8, and -10) are processed in cell-free extracts in response to cytochrome c, and that three others (caspases-1, -4, and -5) failed to be activated under the same conditions. In vitro association assays confirmed that caspase-9 selectively bound to Apaf-1, whereas caspases-1, -2, -3, -6, -7, -8, and -10 did not. Depletion of caspase-9 from cell extracts abrogated cytochrome c-inducible activation of caspases-2, -3, -6, -7, -8, and -10, suggesting that caspase-9 is required for all of these downstream caspase activation events. Immunodepletion of caspases-3, -6, and -7 from cell extracts enabled us to order the sequence of caspase activation events downstream of caspase-9 and reveal the presence of a branched caspase cascade. Caspase-3 is required for the activation of four other caspases (-2, -6, -8, and -10) in this pathway and also participates in a feedback amplification loop involving caspase-9.

Influence of strain and polycrystalline ordering on magnetic properties of high moment rare earth metals and alloys

Despite being the most suitable candidates for solenoid pole pieces in state-of-the-art superconductor- based electromagnets, the intrinsic magnetic properties of heavy rare earth metals and their alloys have gained comparatively little attention. With the potential of integration in micro- and nanoscale devices, thin films of Gd, Dy, Tb, DyGd and DyTb were plasma-sputtered and investigated for their in-plane magnetic properties, with an emphasis on magnetisation vs. temperature profiles. Based on crystal structure analysis of the polycrystalline rare earth films, which consist of a low magnetic moment FCC layer at the seed interface topped with a higher moment HCP layer, an experimental protocol is introduced which allows the direct magnetic analysis of the individual layers. In line with the general trend of heavy lanthanides, the saturation magnetisation was found to drop with increasing unit cell size. In-situ annealed rare earth films exceeded the saturation magnetisation of a high-moment Fe65Co35 reference film in the cryogenic temperature regime, proving their potential for pole piece applications; however as-deposited rare earth films were found completely unsuitable. In agreement with theoretical predictions, sufficiently strained crystal phases of Tb and Dy did not exhibit an incommensurate magnetic order, unlike their single-crystal counterparts which have a helical phase. DyGd and DyTb alloys followed the trends of the elemental rare earth metals in terms of crystal structure and magnetic properties. Inter-rare-earth alloys hence present a desirable blend of saturation magnetisation and operating temperature.