Infrared absorption spectra, radiative efficiencies, and global warming potentials of perfluorocarbons: Comparison between experiment and theory

Experimentally and theoretically determined infrared spectra are reported for a series of straight-chain perfluorocarbons: C2F6, C3F8, C4F10, C5F12, C6F14, and C8F18. Theoretical spectra were determined using both density functional (DFT) and ab initio methods. Radiative efficiencies (REs) were determined using the method of Pinnock et al. (1995) and combined with atmospheric lifetimes from the literature to determine global warming potentials (GWPs). Theoretically determined absorption cross sections were within 10% of experimentally determined values. Despite being much less computationally expensive, DFT calculations were generally found to perform better than ab initio methods. There is a strong wavenumber dependence of radiative forcing in the region of the fundamental C-F vibration, and small differences in wavelength between band positions determined by theory and experiment have a significant impact on the REs. We apply an empirical correction to the theoretical spectra and then test this correction on a number of branched chain and cyclic perfluoroalkanes. We then compute absorption cross sections, REs, and GWPs for an additional set of perfluoroalkenes.

A comparison of extreme value theory approaches for determining value at risk

This paper compares a number of different extreme value models for determining the value at risk (VaR) of three LIFFE futures contracts. A semi-nonparametric approach is also proposed, where the tail events are modeled using the generalised Pareto distribution, and normal market conditions are captured by the empirical distribution function. The value at risk estimates from this approach are compared with those of standard nonparametric extreme value tail estimation approaches, with a small sample bias-corrected extreme value approach, and with those calculated from bootstrapping the unconditional density and bootstrapping from a GARCH(1,1) model. The results indicate that, for a holdout sample, the proposed semi-nonparametric extreme value approach yields superior results to other methods, but the small sample tail index technique is also accurate.

A simple analysis of thermodynamic properties for classical plasmas: I. theory

By eliminating the short range negative divergence of the Debye–Hückel pair distribution function, but retaining the exponential charge screening known to operate at large interparticle separation, the thermodynamic properties of one-component plasmas of point ions or charged hard spheres can be well represented even in the strong coupling regime. Predicted electrostatic free energies agree within 5% of simulation data for typical Coulomb interactions up to a factor of 10 times the average kinetic energy. Here, this idea is extended to the general case of a uniform ionic mixture, comprising an arbitrary number of components, embedded in a rigid neutralizing background. The new theory is implemented in two ways: (i) by an unambiguous iterative algorithm that requires numerical methods and breaks the symmetry of cross correlation functions; and (ii) by invoking generalized matrix inverses that maintain symmetry and yield completely analytic solutions, but which are not uniquely determined. The extreme computational simplicity of the theory is attractive when considering applications to complex inhomogeneous fluids of charged particles.

Formal theory building for the avalanche game: explaining counter-intuitive behaviour of a complex system using geometrical and human behavioural/physiological effects

In 'Avalanche', an object is lowered, players staying in contact throughout. Normally the task is easily accomplished. However, with larger groups counter-intuitive behaviours appear. The paper proposes a formal theory for the underlying causal mechanisms. The aim is to not only provide an explicit, testable hypothesis for the source of the observed modes of behaviour-but also to exemplify the contribution that formal theory building can make to understanding complex social phenomena. Mapping reveals the importance of geometry to the Avalanche game; each player has a pair of balancing loops, one involved in lowering the object, the other ensuring contact. For more players, sets of balancing loops interact and these can allow dominance by reinforcing loops, causing the system to chase upwards towards an ever-increasing goal. However, a series of other effects concerning human physiology and behaviour (HPB) is posited as playing a role. The hypothesis is therefore rigorously tested using simulation. For simplicity a 'One Degree of Freedom' case is examined, allowing all of the effects to be included whilst rendering the analysis more transparent. Formulation and experimentation with the model gives insight into the behaviours. Multi-dimensional rate/level analysis indicates that there is only a narrow region in which the system is able to move downwards. Model runs reproduce the single 'desired' mode of behaviour and all three of the observed 'problematic' ones. Sensitivity analysis gives further insight into the system's modes and their causes. Behaviour is seen to arise only when the geometric effects apply (number of players greater than degrees of freedom of object) in combination with a range of HPB effects. An analogy exists between the co-operative behaviour required here and various examples: conflicting strategic objectives in organizations; Prisoners' Dilemma and integrated bargaining situations. Additionally, the game may be relatable in more direct algebraic terms to situations involving companies in which the resulting behaviours are mediated by market regulations. Finally, comment is offered on the inadequacy of some forms of theory building and the case is made for formal theory building involving the use of models, analysis and plausible explanations to create deep understanding of social phenomena.

Making sense of survival: refining the treatment of state preferences in neorealist theory

The assumption that ‘states' primary goal is survival’ lies at the heart of the neorealist paradigm. A careful examination of the assumption, however, reveals that neorealists draw upon a number of distinct interpretations of the ‘survival assumption’ that are then treated as if they are the same, pointing towards conceptual problems that surround the treatment of state preferences. This article offers a specification that focuses on two questions that highlight the role and function of the survival assumption in the neorealist logic: (i) what do states have to lose if they fail to adopt self-help strategies?; and (ii) how does concern for relevant losses motivate state behaviour and affect international outcomes? Answering these questions through the exploration of governing elites' sensitivity towards regime stability and territorial integrity of the state, in turn, addresses the aforementioned conceptual problems. This specification has further implications for the debates among defensive and offensive realists, potential extensions of the neorealist logic beyond the Westphalian states, and the relationship between neorealist theory and policy analysis.

A unified theory of balance in the extratropics

Many physical systems exhibit dynamics with vastly different time scales. Often the different motions interact only weakly and the slow dynamics is naturally constrained to a subspace of phase space, in the vicinity of a slow manifold. In geophysical fluid dynamics this reduction in phase space is called balance. Classically, balance is understood by way of the Rossby number R or the Froude number F; either R ≪ 1 or F ≪ 1. We examined the shallow-water equations and Boussinesq equations on an f -plane and determined a dimensionless parameter _, small values of which imply a time-scale separation. In terms of R and F, ∈= RF/√(R^2+R^2 ) We then developed a unified theory of (extratropical) balance based on _ that includes all cases of small R and/or small F. The leading-order systems are ensured to be Hamiltonian and turn out to be governed by the quasi-geostrophic potential-vorticity equation. However, the height field is not necessarily in geostrophic balance, so the leading-order dynamics are more general than in quasi-geostrophy. Thus the quasi-geostrophic potential-vorticity equation (as distinct from the quasi-geostrophic dynamics) is valid more generally than its traditional derivation would suggest. In the case of the Boussinesq equations, we have found that balanced dynamics generally implies hydrostatic balance without any assumption on the aspect ratio; only when the Froude number is not small and it is the Rossby number that guarantees a timescale separation must we impose the requirement of a small aspect ratio to ensure hydrostatic balance.

Wave-activity conservation laws and stability theorems for semi-geostrophic dynamics: part 2. pseudoenergy-based theory

This paper represents the second part of a study of semi-geostrophic (SG) geophysical fluid dynamics. SG dynamics shares certain attractive properties with the better known and more widely used quasi-geostrophic (QG) model, but is also a good prototype for balanced models that are more accurate than QG dynamics. The development of such balanced models is an area of great current interest. The goal of the present work is to extend a central body of QG theory, concerning the evolution of disturbances to prescribed basic states, to SG dynamics. Part 1 was based on the pseudomomentum; Part 2 is based on the pseudoenergy. A pseudoenergy invariant is a conserved quantity, of second order in disturbance amplitude relative to a prescribed steady basic state, which is related to the time symmetry of the system. We derive such an invariant for the semi-geostrophic equations, and use it to obtain: (i) a linear stability theorem analogous to Arnol'd's ‘first theorem’; and (ii) a small-amplitude local conservation law for the invariant, obeying the group-velocity property in the WKB limit. The results are analogous to their quasi-geostrophic forms, and reduce to those forms in the limit of small Rossby number. The results are derived for both the f-plane Boussinesq form of semi-geostrophic dynamics, and its extension to β-plane compressible flow by Magnusdottir & Schubert. Novel features particular to semi-geostrophic dynamics include apparently unnoticed lateral boundary stability criteria. Unlike the boundary stability criteria found in the first part of this study, however, these boundary criteria do not necessarily preclude the construction of provably stable basic states. The interior semi-geostrophic dynamics has an underlying Hamiltonian structure, which guarantees that symmetries in the system correspond naturally to the system's invariants. This is an important motivation for the theoretical approach used in this study. The connection between symmetries and conservation laws is made explicit using Noether's theorem applied to the Eulerian form of the Hamiltonian description of the interior dynamics.

Wave-activity conservation laws and stability theorems for semi-geostrophic dynamics: part 1. pseudomomentum-based theory

There exists a well-developed body of theory based on quasi-geostrophic (QG) dynamics that is central to our present understanding of large-scale atmospheric and oceanic dynamics. An important question is the extent to which this body of theory may generalize to more accurate dynamical models. As a first step in this process, we here generalize a set of theoretical results, concerning the evolution of disturbances to prescribed basic states, to semi-geostrophic (SG) dynamics. SG dynamics, like QG dynamics, is a Hamiltonian balanced model whose evolution is described by the material conservation of potential vorticity, together with an invertibility principle relating the potential vorticity to the advecting fields. SG dynamics has features that make it a good prototype for balanced models that are more accurate than QG dynamics. In the first part of this two-part study, we derive a pseudomomentum invariant for the SG equations, and use it to obtain: (i) linear and nonlinear generalized Charney–Stern theorems for disturbances to parallel flows; (ii) a finite-amplitude local conservation law for the invariant, obeying the group-velocity property in the WKB limit; and (iii) a wave-mean-flow interaction theorem consisting of generalized Eliassen–Palm flux diagnostics, an elliptic equation for the stream-function tendency, and a non-acceleration theorem. All these results are analogous to their QG forms. The pseudomomentum invariant – a conserved second-order disturbance quantity that is associated with zonal symmetry – is constructed using a variational principle in a similar manner to the QG calculations. Such an approach is possible when the equations of motion under the geostrophic momentum approximation are transformed to isentropic and geostrophic coordinates, in which the ageostrophic advection terms are no longer explicit. Symmetry-related wave-activity invariants such as the pseudomomentum then arise naturally from the Hamiltonian structure of the SG equations. We avoid use of the so-called ‘massless layer’ approach to the modelling of isentropic gradients at the lower boundary, preferring instead to incorporate explicitly those boundary contributions into the wave-activity and stability results. This makes the analogy with QG dynamics most transparent. This paper treats the f-plane Boussinesq form of SG dynamics, and its recent extension to β-plane, compressible flow by Magnusdottir & Schubert. In the limit of small Rossby number, the results reduce to their respective QG forms. Novel features particular to SG dynamics include apparently unnoticed lateral boundary stability criteria in (i), and the necessity of including additional zonal-mean eddy correlation terms besides the zonal-mean potential vorticity fluxes in the wave-mean-flow balance in (iii). In the companion paper, wave-activity conservation laws and stability theorems based on the SG form of the pseudoenergy are presented.

A unified theory of available potential energy

Traditional derivations of available potential energy, in a variety of contexts, involve combining some form of mass conservation together with energy conservation. This raises the questions of why such constructions are required in the first place, and whether there is some general method of deriving the available potential energy for an arbitrary fluid system. By appealing to the underlying Hamiltonian structure of geophysical fluid dynamics, it becomes clear why energy conservation is not enough, and why other conservation laws such as mass conservation need to be incorporated in order to construct an invariant, known as the pseudoenergy, that is a positive‐definite functional of disturbance quantities. The available potential energy is just the non‐kinetic part of the pseudoenergy, the construction of which follows a well defined algorithm. Two notable features of the available potential energy defined thereby are first, that it is a locally defined quantity, and second, that it is inherently definable at finite amplitude (though one may of course always take the small‐amplitude limit if this is appropriate). The general theory is made concrete by systematic derivations of available potential energy in a number of different contexts. All the well known expressions are recovered, and some new expressions are obtained. The possibility of generalizing the concept of available potential energy to dynamically stable basic flows (as opposed to statically stable basic states) is also discussed.

Interpersonal interaction and economic theory: the case of public goods

Interpersonal interaction in public goods contexts is very different in character to its depiction in economic theory, despite the fact that the standard model is based on a small number of apparently plausible assumptions. Approaches to the problem are reviewed both from within and outside economics. It is argued that quick fixes such as a taste for giving do not provide a way forward. An improved understanding of why people contribute to such goods seems to require a different picture of the relationships between individuals than obtains in standard microeconomic theory, where they are usually depicted as asocial. No single economic model at present is consistent with all the relevant field and laboratory data. It is argued that there are defensible ideas from outside the discipline which ought to be explored, relying on different conceptions of rationality and/or more radically social agents. Three such suggestions are considered, one concerning the expressive/communicative aspect of behaviour, a second the possibility of a part-whole relationship between interacting agents and the third a version of conformism.

Analysing the factors that influence tag choice based on semiotic analysis and activity theory

Social tagging has become very popular around the Internet as well as in research. The main idea behind tagging is to allow users to provide metadata to the web content from their perspective to facilitate categorization and retrieval. There are many factors that influence users' tag choice. Many studies have been conducted to reveal these factors by analysing tagging data. This paper uses two theories to identify these factors, namely the semiotics theory and activity theory. The former treats tags as signs and the latter treats tagging as an activity. The paper uses both theories to analyse tagging behaviour by explaining all aspects of a tagging system, including tags, tagging system components and the tagging activity. The theoretical analysis produced a framework that was used to identify a number of factors. These factors can be considered as categories that can be consulted to redirect user tagging choice in order to support particular tagging behaviour, such as cross-lingual tagging.

Health care rights and NHS rationing: turning theory into practice

How should we understand the nature of patients’ right in public health care systems? Are health care rights different to rights under a private contract for car insurance? This article distinguishes between public and private rights and the relevance of community interests and notions of social solidarity. It discusses the distinction between political and civil rights, and social and economic rights and the inherently political and redistributive nature of the latter. Nevertheless, social and economic rights certainly give rise to “rights” enforceable by the courts. In the UK (as in many other jurisdictions), the courts have favoured a “procedural” approach to the question, in which the courts closely scrutinise decisions and demand high standards of rationality from decision-makers. However, although this is the general rule, the article also discusses a number of exceptional cases where “substantive” remedies are available which guarantee patients access to the care they need.