Surface and interstitial Ti diffusion at the rutile TiO2(110) surface

Diffusion of Ti through the TiO2 (110) rutile surface plays a key role in the growth and reactivity of TiO2. To understand the fundamental aspects of this important process, we present an analysis of the diffusion of Ti adspecies at the stoichiometric TiO2(110) surface using complementary computational methodologies of density functional theory corrected for on-site Coulomb interactions (DFT+U) and a charge equilibration (QEq) atomistic potential to identify minimum energy pathways. We find that diffusion of Ti from the surface to subsurface (and vice versa) follows an intersticialcy exchange mechanism, involving exchange of surface Ti with the 6-fold coordinated Ti below the bridging oxygen rows. Diffusion in the subsurface between layers also follows an interstitialcy mechanism. The diffusion of Ti is discussed in light of continued attempts to understand the re-oxidation of non-stoichiometric TiO2(110) surfaces.

The British ‘failure’ that never was? The Anglo-American ‘productivity gap’ in large-scale interwar retailing—evidence from the department store sector

Interwar British retailing has been characterized as having lower productivity, less developed managerial hierarchies and methods, and weaker scale economies than its US counterpart. This article examines comparative productivity for one major segment of large-scale retailing in both countries—the department store sector. Drawing on exceptionally detailed contemporary survey data, we show that British department stores in fact achieved superior performance in terms of operating costs, margins, profits, and stock-turn. While smaller British stores had lower labour productivity than US stores of equivalent size, TFP was generally higher for British stores, which also enjoyed stronger scale economies. We also examine the reasons behind Britain's surprisingly strong relative performance, using surviving original returns from the British surveys. Contrary to arguments that British retailers faced major barriers to the development of large-scale enterprises, that could reap economies of scale and scope and invest in machinery and marketing to support the growth of their primary sales functions, we find that British department stores enthusiastically embraced the retail ‘managerial revolution’—and reaped substantial benefits from this investment.

Demand, supply and willingness-to-pay for extension services in an emerging-market setting

Although it may be wholly inappropriate to generalize, the most important resource available to a subsistence household is the total amount of time that its members have available to spend in productive enterprises. In this context, services that minimize the time that it takes to perform productive activities are valuable to the household. Consequently the household is willing to relinquish quantities of other resources in exchange for quantities of the time-saving service. These simple observations motivate a search for the values that subsistence households place on time-saving services. This search is especially important when it is realized that extension services promote productivity, enhance the surplus-generating potential of the household and can, as a consequence, promote immersion into markets that are currently constrained by thinness and instability. In this capacity, extension visitation has the potential to overcome one of the principal impediments to economic development, namely lack of density of market participation. In this article, we consider this issue in the context of a rich data set on milk-market participation by small-holder dairy producers in the Ethiopian highlands.

Economic commodity or environmental crisis? An interdisciplinary approach to analysing the bushmeat trade in central and west Africa

Bushmeat is a large but largely invisible contributor to the economies of west and central African countries. Yet the trade is currently unsustainable. Hunting is reducing wildlife populations, driving more vulnerable species to local and regional extinction, and threatening biodiversity. This paper uses a commodity chain approach to explore the bushmeat trade and to demonstrate why an interdisciplinary approach is required if the trade is to be sustainable in the future.

Phase separation and surface segregation in ceria-zirconia solid solutions

Using a combination of density functional theory calculations and statistical mechanics, we show that a wide range of intermediate compositions of ceria – zirconia solid solutions are thermodynamically metastable with respect to phase separation into Ce-rich and Zr-rich oxides. We estimate that the maximum equilibrium concentration of Zr in CeO2 at 1373 K is ~2%, and therefore equilibrated samples with higher Zr content are expected to exhibit heterogeneity at the atomic scale. We also demonstrate that in the vicinity of the (111) surface, cation redistribution at high temperatures will occur with significant Ce enrichment of the surface, which we attribute to the more covalent character of Zr-O bonds compared to Ce-O bonds. Although the kinetic barriers for cation diffusion normally prevent the decomposition/segregation of ceria-zirconia solid solutions in typical catalytic applications, the separation behaviour described here can be expected to occur in modern three-way catalytic converters, where very high temperatures are reached.

Money laundering and the shadow economy in Kazakhstan

Purpose The purpose of this paper is to assess and highlight the approach taken towards the legal control of illicit money laundering taken in the Republic of Kazakhstan, in particular, the role played by an amnesty on the legalisation of illicit funds. This is particularly important as a basis for a wider discussion about the proper limits of the “criminalising” approaches commonly taken in anti-money laundering regulations. Design/methodology/approach The discussion and evaluation in the paper is based upon a conceptual analysis of the money laundering regime in Kazakhstan, in particular, the legal framework and policies of implementation adopted. Findings The paper demonstrates that the problems that are posed by the shadow economy in post-Soviet transition societies can make the blanket criminalisation of money laundering a self-defeating approach, unless accompanied by measures which allow for the achievement of “market-constituting” effects. Research limitations/implications The paper draws on experience and practice in one jurisdiction only (Kazakhstan); it also limits its focus to one particular example of a money laundering amnesty policy. Both of these limitations, therefore, suggest avenues for further comparative research. Originality/value The paper’s conclusions about the interactions between the shadow economies of transitional societies and the global anti-money laundering agenda have wider application in assessments of international law in this area.

The cleft ion fountain: a two-dimensional kinetic model

The transport of ionospheric ions from a source in the polar cleft ionosphere through the polar magnetosphere is investigated using a two-dimensional, kinetic, trajectory-based code. The transport model includes the effects of gravitation, longitudinal magnetic gradient force, convection electric fields, and parallel electric fields. Individual ion trajectories as well as distribution functions and resulting bulk parameters of density, parallel average energy, and parallel flux for a presumed cleft ionosphere source distribution are presented for various conditions to illustrate parametrically the dependences on source energies, convection electric field strengths, ion masses, and parallel electric field strengths. The essential features of the model are consistent with the concept of a cleft-based ion fountain supplying ionospheric ions to the polar magnetosphere, and the resulting plasma distributions and parameters are in general agreement with recent low-energy ion measurements from the DE 1 satellite.

Balanced Ocean-Data Assimilation near the Equator

The question is addressed whether using unbalanced updates in ocean-data assimilation schemes for seasonal forecasting systems can result in a relatively poor simulation of zonal currents. An assimilation scheme, where temperature observations are used for updating only the density field, is compared to a scheme where updates of density field and zonal velocities are related by geostrophic balance. This is done for an equatorial linear shallow-water model. It is found that equatorial zonal velocities can be detoriated if velocity is not updated in the assimilation procedure. Adding balanced updates to the zonal velocity is shown to be a simple remedy for the shallow-water model. Next, optimal interpolation (OI) schemes with balanced updates of the zonal velocity are implemented in two ocean general circulation models. First tests indicate a beneficial impact on equatorial upper-ocean zonal currents.

Sea ice production and water mass modification in the eastern Laptev Sea

A simple polynya flux model driven by standard atmospheric forcing is used to investigate the ice formation that took place during an exceptionally strong and consistent western New Siberian (WNS) polynya event in 2004 in the Laptev Sea. Whether formation rates are high enough to erode the stratification of the water column beneath is examined by adding the brine released during the 2004 polynya event to the average winter density stratification of the water body, preconditioned by summers with a cyclonic atmospheric forcing (comparatively weakly stratified water column). Beforehand, the model performance is tested through a simulation of a well‐documented event in April 2008. Neglecting the replenishment of water masses by advection into the polynya area, we find the probability for the occurrence of density‐driven convection down to the bottom to be low. Our findings can be explained by the distinct vertical density gradient that characterizes the area of the WNS polynya and the apparent lack of extreme events in the eastern Laptev Sea. The simple approach is expected to be sufficiently rigorous, since the simulated event is exceptionally strong and consistent, the ice production and salt rejection rates are likely to be overestimated, and the amount of salt rejected is distrusted over a comparatively weakly stratified water column. We conclude that the observed erosion of the halocline and formation of vertically mixed water layers during a WNS polynya event is therefore predominantly related to wind‐ and tidally driven turbulent mixing processes.

Simulating decadal variability in the North Atlantic Ocean

Observations and climate models suggest significant decadal variability within the North Atlantic subpolar gyre (NA SPG), though observations are sparse and models disagree on the details of this variability. Therefore, it is important to understand 1) the mechanisms of simulated decadal variability, 2) which parts of simulated variability are more faithful representations of reality, and 3) the implications for climate predictions. Here, we investigate the decadal variability in the NA SPG in the state-of-the-art, high resolution (0.25◦ ocean resolution), climate model ‘HadGEM3’. We find a decadal mode with a period of 17 years that explains 30% of the annual variance in related indices. The mode arises due to the advection of heat content anomalies, and shows asymmetries in the timescale of phase reversal between positive and negative phases. A negative feedback from temperature-driven density anomalies in the Labrador Sea (LS) allows for the phase reversal. The North Atlantic Oscillation (NAO), which exhibits the same periodicity, amplifies the mode. The atmosphere-ocean coupling is stronger during positive rather than negative NAO states, explaining the asymmetry. Within the NA SPG, there is potential predictability arising partly from this mode for up to 5 years. There are important similarities between observed and simulated variability, such as the apparent role for the propagation of heat content anomalies. However, observations suggest interannual LS density anomalies are salinity-driven. Salinity control of density would change the temperature feedback to the south, possibly limiting real-world predictive skill in the southern NA SPG with this model. Finally, to understand the diversity of behaviours, we analyse 42 present-generation climate models. Temperature and salinity biases are found to systematically influence the driver of density variability in the LS. Resolution is a good predictor of the biases. The dependence of variability on the background state has important implications for decadal predictions.

Hyperfine interaction studies with (181)Ta and (111)Cd probes in the compound Ti(2)Ag

By using the time-differential perturbed angular correlation technique, the electric field gradients (EFG) at (181)Hf/(181)Ta and (111)In/(111)Cd probe sites in the MoSi(2)-type compound Ti(2)Ag have been measured as a function of temperature in the range from 24 to 1073 K. Ab initio EFG calculations have been performed within the framework of density functional theory using the full-potential augmented plane wave + local orbitals method as implemented in the WIEN2k package. These calculations allowed assignments of the probe lattice sites. For Ta, a single well-defined EFG with very weak temperature dependence was established and attributed to the [4(e)4mm] Ti site. For (111)Cd probes, two of the three measured EFGs are well defined and correlated with substitutional lattice sites, i.e. both the [4(e)4mm] Ti site and the [2(a)4/mmm] Ag site.

Entanglement degree measure and a criterion for sudden death as a phase transition in bipartite systems

We propose a method to compute the entanglement degree E of bipartite systems having dimension 2 x 2 and demonstrate that the partial transposition of density matrix, the Peres criterion, arise as a consequence Of Our method. Differently from other existing measures of entanglement, the one presented here makes possible the derivation of a criterion to verify if an arbitrary bipartite entanglement will suffers sudden death (SD) based only on the initial-state parameters. Our method also makes possible to characterize the SD as a dynamical quantum phase transition, with order parameter epsilon. having a universal critical exponent -1/2. (C) 2009 Elsevier Inc. All rights reserved.

Entry, re-location and growth in the Swedish wholesale trade industry

Wholesale trade has an intermediate position between manufacturing and retail in the distributional channel. In modern economies, consumers buy few, if any, products directly from manufacture or producer. Instead, it is a wholesaler, who is in direct contact with producers, buying goods in larger quantities and selling them in smaller quantities to retailers. Traditionally, the main function of a wholesaler has been to push goods along the distributional channel from producer to retailer, or other nonend user. However, the function of wholesalers usually goes beyond the process of the physical distribution of goods. Wholesalers also arrange storage, perform market analyses, promote trade or provide technical support to consumers (Riemers 1998). The existence of wholesalers (and other intermediaries) in the distributional channel is based on the effective and efficient performance of distribution services, that are needed by producers and other members of the supply chain. Producers usually do not enjoy the economies of scale that they have in production, when it comes to providing distributional services (Rosenbloom 2007) and this creates a space for wholesalers or other intermediaries. Even though recent developments in the distributional channel indicate that traditional wholesaling activities now also compete with other supply chain organizations, wholesaling still remains an important activity in many economies (Quinn and Sparks, 2007). In 2010, the Swedish wholesale trade sector consisted of approximately 46.000 firms and generated an annual turnover of 1 300 billion SEK (Företagsstatistiken, Statistics Sweden). In terms of turnover, wholesaling accounts for 20% of the gross domestic product and is thereby the third largest industry. This is behind manufacturing and a composite group of firms in other sectors of the service industry but ahead of retailing. This indicates that the wholesale trade sector is an important part of the Swedish economy. The position of wholesaling is further reinforced when measuring productivity growth. Measured in terms of value added per employee, wholesaling experienced the largest productivity growth of all industries in the Swedish economy during the years 2000 through 2010. The fact that wholesale trade is one of the important parts of a modern economy, and the positive development of the Swedish wholesale trade sector in recent decades, leads to several questions related to industry dynamics. The three topics that will be examined in this thesis are firm entry, firm relocation and firm growth. The main question to be answered by this thesis is what factors influence new firm formation, firm relocation and firm growth in the Swedish wholesale trade sector?

Gravitational self-localization for spherical masses

In this work, I consider the center-of-mass wave function for a homogenous sphere under the influence of the self-interaction due to Newtonian gravity. I solve for the ground state numerically and calculate the average radius as a measure of its size. For small masses, M≲10−17 kg, the radial size is independent of density, and the ground state extends beyond the extent of the sphere. For masses larger than this, the ground state is contained within the sphere and to a good approximation given by the solution for an effective radial harmonic-oscillator potential. This work thus determines the limits of applicability of the point-mass Newton Schrödinger equations for spherical masses. In addition, I calculate the fringe visibility for matter-wave interferometry and find that in the low-mass case, interferometry can in principle be performed, whereas for the latter case, it becomes impossible. Based on this, I discuss this transition as a possible boundary for the quantum-classical crossover, independent of the usually evoked environmental decoherence. The two regimes meet at sphere sizes R≈10−7 m, and the density of the material causes only minor variations in this value.