The dissociation of molecularly adsorbed CO and CN over the 4d transition metals: A universal relationship between the reaction barriers and the reaction enthalpies

Density functional theory calculations are used to study the stability of molecularly adsorbed CO and CN over transition metal surfaces. The minimum energy reaction pathways, corresponding reaction barriers (E-a), and reaction enthalpies (Delta H) for the dissociation of CO and CN to atomic products over the 4d transition metals from Zr to Pd have been determined. CO is found to be the more stable adsorbate on the right hand side of the period (from Tc onwards), whereas CN is the more stable surface species on the early metals (Zr, Nb and Mo). A single linear relationship is found to exist that correlates the barriers of both reactions with their respective reaction enthalpies. (c) 2006 Elsevier B.V. All rights reserved.

Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces

The dissociative adsorption of N-2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

Reactivity of the 4d transition metals toward N hydrogenation and NH dissociation: A DFT-based HSAB analysis

The density functional theory (DFT) based hard-soft acid-base (HSAB) reactivity indices, including the electrophilicity index, have been successfully applied to many areas of molecular chemistry. In this work we test the applicability of such an approach to fundamental surface chemistry. We have considered, as prototypical surface reactions, both the hydrogenation of atomic nitrogen and the dissociative adsorption of the NH molecular radical. By use of a DFT methodology, the minimum energy reaction pathways, and corresponding reaction barriers, of the above reactions over Zr(001), Nb(110), Mo(110), Tc(001), Ru(001), Rh(111), and Pd(111) have been determined. By consideration of the chemical potential and chemical hardness of the surface metal atoms, and the principle of electronegativity equalization, it is found that the charge transferred to the NH radical during the process of dissociative adsorption correlates very well with that determined by Mulliken population analysis. Furthermore, it is found that the stability of the NH/surface transition state complex relates directly to this charge transfer and that the trend in transition state stability predicted by a HSAB; treatment correlates very strongly with that determined by DFT calculations. With regards to N hydrogenation, we find that during the course of the reaction, H loses cohesion to the surface, as it must migrate from a 3-fold hollow site to either a bridge or top site, to react with N. Partial density of states (PDOS) and Mulliken population analysis reveal that this loss of bonding is accompanied by charge transfer from H to the surface metal atoms. Moreover, by simple modeling, we show that the reaction barriers are directly proportional to this mandatory charge transfer. Indeed, it is found that the reaction barriers correlate very well with the electrophilicity index of the metal atoms.

The importance of hydrogen's potential-energy surface and the strength of the forming R-H bond in surface hydrogenation reactions

An understanding of surface hydrogenation reactivity is a prevailing issue in chemistry and vital to the rational design of future catalysts. In this density-functional theory study, we address hydrogenation reactivity by examining the reaction pathways for N+H -> NH and NH+H -> NH2 over the close-packed surfaces of the 4d transition metals from Zr-Pd. It is found that the minimum-energy reaction pathway is dictated by the ease with which H can relocate between hollow-site and top-site adsorption geometries. A transition state where H is close to a top site reduces the instability associated with bond sharing of metal atoms by H and N (NH) (bonding competition). However, if the energy difference between hollow-site and top-site adsorption energies (Delta E-H) is large this type of transition state is unfavorable. Thus we have determined that hydrogenation reactivity is primarily controlled by the potential-energy surface of H on the metal, which is approximated by Delta E-H, and that the strength of N (NH) chemisorption energy is of less importance. Delta E-H has also enabled us to make predictions regarding the structure sensitivity of these reactions. Furthermore, we have found that the degree of bonding competition at the transition state is responsible for the trend in reaction barriers (E-a) across the transition series. When this effect is quantified a very good linear correlation is found with E-a. In addition, we find that when considering a particular type of reaction pathway, a good linear correlation is found between the destabilizing effects of bonding competition at the transition state and the strength of the forming N-H (HN-H) bond. (c) 2006 American Institute of Physics.

General trends in the barriers of catalytic reactions on transition metal surfaces

A catalyst preparation by design is one of the ultimate goals in chemistry. The first step towards this goal is to understand the origin of reaction barriers. In this study, we have investigated several catalytic reactions on some transition metal surfaces, using density functional theory. All the reaction barriers have been determined. By detailed analyses we obtain some insight into the reaction barrier. Each barrier is related to (i) the potential energy surface of reactants on the surface, (ii) the total chemisorption energy of reactants, and (iii) the metal d orbital occupancy and the reactant valency. (C) 2001 American Institute of Physics.

General trends in CO dissociation on transition metal surfaces

Dissociative adsorption is one of the most important reactions in catalysis. In this communication we propose a model aiming to generalize the important factors that affect dissociation reactions. Specifically, for a dissociation reaction, say AB -->A + B, the model connects the dissociation barrier with the association barrier, the chemisorption energies of A and B at the final state and the bonding energy of AB in the gas phase. To apply this model, we have calculated CO dissociation on Ru(0001), Rh(111), Pd(111) (4d transition metals), Os(0001), Ir(111), and Pt(111) (5d transition metals) using density function theory (DFT). All the barriers are determined. We find that the DFT results can be rationalized within the model. The model can also be used to explain many experimental observations. (C) 2001 American Institute of Physics.

'Ulster's policing goes global': The police reform process in Northern Ireland and the creation of a global brand

This paper engages with contemporary discussions in relation to the commodification of policing and security. It suggests that the existing literature regarding these trends has been geared primarily towards commercial security providers and has failed to address the processes by which public policing models are commodified and marketed both within, and through, the transnational policing community. Drawing upon evidence from the police change process in Northern Ireland, we argue that a Northern Irish Policing Model (NIPM) has emerged in the aftermath of the Independent Commission on Policing (ICP) reforms. This is increasingly branded and promoted on the global stage. Furthermore, we suggest that the NIPM is not monolithic, but segmented, and targeted towards a number of different 'consumers' both domestically and transnationally. Reflecting these diverse markets, the NIPM draws upon two seemingly incongruous constituent elements: the 'best practice' lessons of policing transition, as embodied in the ICP reforms; and, the legacy of counter-terrorism expertise drawn from the preceding decades of conflict. The discussion concludes by querying as to which of these components of the NIPM is in the ascendancy.

What Happened to the ‘Development’ in Sustainable Development? Business Guidelines Two Decades After Brundtland

Over twenty years ago ‘Our Common Future’ presented a conceptualization and explanation of the concept of sustainable development. Since then numerous alternative definitions of the concept have been offered, of which at least some are exclusive to each other. At the same time, the role of business in the transition to sustainable development has increasingly received attention. Bringing these two trends in sustainable development together, this paper returns to the Brundtland version of the concept to examine to what extent the original principles of sustainable development are still embedded within key business guidelines, namely the UN Global Compact, the OECD Guidelines for Multinational Enterprises, the ICC Business Charter for Sustainable Development, the CAUX Principles, the Global Sullivan Principles and the CERES Principles. The findings suggest that these business guidelines tend to emphasize environmental rather than social aspects of sustainable development, in particular to the detriment of the original Brundtland prioritization of the needs of the poorest. Furthermore, the attention to environmental aspects stresses win-win situations and has a clear managerialist focus; whereas more conceptual environmental issues concerning systems interdependencies, critical thresholds or systemic limits to growth find little attention. The normative codes and principles targeted at the private sector thus not only add another voice to the multiple discourses on sustainable development but also contribute to a reinterpretation of the original agenda set by Brundtland towards conceptualizations of sustainable development around the needs of industrialised rather than developing countries. Copyright © 2011 John Wiley & Sons, Ltd and ERP Environment

Decay of Cystalline Order and Equilibration during the Solid-to-Plasma Transition Induced by 20-fs Microfocused 92-eV Free-Electron-Laser Pulses

We have studied a solid-to-plasma transition by irradiating Al foils with the FLASH free electron laser at intensities up to 10(16) W/cm(2). Intense XUV self-emission shows spectral features that are consistent with emission from regions of high density, which go beyond single inner-shell photoionization of solids. Characteristic features of intrashell transitions allowed us to identify Auger heating of the electrons in the conduction band occurring immediately after the absorption of the XUV laser energy as the dominant mechanism. A simple model of a multicharge state inverse Auger effect is proposed to explain the target emission when the conduction band at solid density becomes more atomiclike as energy is transferred from the electrons to the ions. This allows one to determine, independent of plasma simulations, the electron temperature and density just after the decay of crystalline order and to characterize the early time evolution.

Using low and high prepulses to enhance the J=0-1 transition at 19.6 nm in the Ne-like germanium XUV laser

We report a study of the effect of prepulses on XUV lasing of Ne-like germanium for an irradiation geometry where approximate to 20 mm long germanium slab targets were irradiated at approximate to 1.6 x 10(13) W cm(-2) using approximate to 0.7 ns (1.06 mu m) pulses from the VULCAN glass laser. Prepulses were generated at fractional power levels of approximate to 2 x 10(-4) (low) and approximate to 2 x 10(-2) (high) and arrived on target 5 and 3.2 ns respectively in advance of the main heating pulse, For both the low and high prepulses the output of the 3p-3s, J = 0-1, line at 19.6 nm was enhanced such that the peak radiant density (J/st) for this line became greater than that for the normally stronger J = 2-1 lines at 23.2 and 23.6 nm. The J = 0-1 line, whose FWHM duration was reduced from approximate to 450 ps to approximate to 100 ps, delivered approximate to 6 x more power (W) than the average for the combined J = 2-1 lines, whose FWHM duration was approximate to 500 ps for both levels of prepulse, The higher prepulse was more effective, yielding approximate to 2 x more radiant density and approximate to 7 x more power on both the J = 0-1 and J = 2-1 transitions compared to the low prepulse case, The most dramatic observation overall was the approximate to 40 x increase of power in the J = 0-1 line for the high prepulse (approximate to 2%) case compared with the zero prepulse case. These observations, coupled with measurements of beam divergence and beam deviation through refractive bending, as well as general agreement with modelling, lead us to conclude that, for germanium, the main influence of the prepulse is (a) to increase the energy absorbed from the main pulse, (b) to increase the volume of the gain zone and (c) to relax the plasma density gradients, particularly in the J = 0-1 gain zone.

Global change alters the stability of food webs

Recent research has generally shown that a small change in the number of species in a food web can have consequences both for community structure and ecosystem processes. However 'change' is not limited to just the number of species in a community, but might include an alteration to such properties as precipitation, nutrient cycling and temperature. How such changes might affect species interactions is important, not just through the presence or absence of interactions, but also because the patterning of interaction strengths among species is intimately associated with community stability. Interaction strengths encompass such properties as feeding rates and assimilation efficiencies, and encapsulate functionally important information with regard to ecosystem processes. Interaction strengths represent the pathways and transfer of energy through an ecosystem. We review the best empirical data available detailing the frequency distribution of interaction strengths in communities. We present the underlying (but consistent) pattern of species interactions and discuss the implications of this patterning. We then examine how such a basic pattern might be affected given various scenarios of 'change' and discuss the consequences for community stability and ecosystem functioning.

How does global change affect the strength of trophic interactions?

Recent research has generally shown that a small change in the number of species in a food web can have consequences both for community structure and ecosystem processes. However 'change' is not limited to just the number of species in a community, but might include an alteration to such properties as precipitation, nutrient cycling and temperature, all of which are correlated with productivity. Here we argue that predicted scenarios of global change will result in increased plant productivity. We model three scenarios of change using simple Lotka-Volterra dynamics, which explore how a global change in productivity might affect the strength of local species interactions and detail the consequences for community and ecosystem level stability. Our results indicate that (i) at local scales the average population size of consumers may decline because of poor quality food resources, (ii) that the strength of species interactions at equilibrium may become weaker because of reduced population size, and (iii) that species populations may become more variable and may take longer to recover from environmental or anthropogenic disturbances. At local scales interaction strengths encompass such properties as feeding rates and assimilation efficiencies, and encapsulate functionatty important information with regard to ecosystem processes. Interaction strengths represent the pathways and transfer of energy through an ecosystem. We examine how such local patterns might be affected given various scenarios of 'global change' and discuss the consequences for community stability and ecosystem functioning. (C) 2004 Elsevier GmbH. All rights reserved.

The contribution of the United Nations Convention on the Rights of the Child to understanding and promoting the interests of young people making the transition from care to adulthood

The United Nations Convention on the Rights of the Child (UNCRC) acknowledges that young people without parental care are entitled to special support and assistance from the State. In detailing their expectations, the UN Committee have issued Guidelines for the Alternative Care of Children which recognise that State parties have a number of responsibilities towards care leavers. The paper explores how the UNCRC reporting process, and guidelines from the Committee outlining how States should promote the rights of young people making the transition from care to adulthood, can be used as an instrument to track global patterns of change in policy and practice. Content analysis of State Party Reports and Concluding Observations from 15 countries reveals that to date there has been limited engagement with understanding and promoting the needs of this group in the reporting process; although where a government is committed to developing legislation and practice then this does find its way into their national reports. Data supplied by affiliates of the International Research Network on Transitions to Adulthood from Care (INTRAC) reveals that national concerns, political ideology, public awareness, attitudes and knowledge of the vulnerability of care leavers influence service responses to protect and promote the rights of this group and the attention afforded to such issues in reports to the Committee. Findings also suggest that global governance is not simply a matter of top down influence. Future work on both promoting and monitoring of the impact of the UNCRC needs to recognise that what is in play is the management of a complex global/national dynamic with all its uneven development, levels of influence and with a range of institutional actors involved.

Energy sustainability indicators for urban environments

Sustainable development comprises of three dimensions. The three dimensions are the environment, the social and the economic. There have been many indicators used to measure the three dimensions of sustainability. For example air pollution, consumption of natural resources, quality of open space, noise, equity and opportunities and economic benefits from transport and land use. Urban areas constitute the most crucial factor in the sustainability. Urban systems affect and are affected by natural systems beyond their physical boundaries and in general the interdependence between the urban system and the regional and global environment is not reflected in urban decision making. The use of energy in the urban system constitutes the major element in the construction and function of urban areas. Energy impacts across the boundaries of the three dimensions of sustainability. The objective of this research is to apply energy-use-indicators to the urban system as a measure of sustainability. This methodology is applied to a case study in the United Kingdom.