Study of the nonlinear optical properties of a crosslinkable chromophore for use in guest host polymer films

A guest/host material system in which the guest molecule is a functionalized, optically nonlinear, chromophore is described. A verification of the crosslinking process, an assessment of the nonlinear properties of the chromophore, using Solvatochromic methods, and an investigation of the electric field induced molecular orientation using second-harmonic generation are included.

A comparison of photoinduced poling and thermal poling of azo‐dye‐doped polymer films for second order nonlinear optical applications

Photoinduced poling (PIP) is a new technique which allows the room‐temperature preparation of guest/host polymer films exhibiting significant polar order for nonlinear optical applications. We report a comparison of this novel technique with the conventional electrode poling procedure performed at the glass transition temperature of the polymer using disperse red 1/poly(methylmethacrylate) films. In particular, in situ second harmonic generation measurements show that levels of polar order achieved using these two techniques are similar. In contrast, the stability of the polar order is reduced by up to 20 times in terms of the decay time constant in films prepared using PIP although the stability is very dependent upon the temperature at which the poling was performed.

Response theory for equilibrium and non-equilibrium statistical mechanics: causality and generalized Kramers-Kronig relations

We consider the general response theory recently proposed by Ruelle for describing the impact of small perturbations to the non-equilibrium steady states resulting from Axiom A dynamical systems. We show that the causality of the response functions entails the possibility of writing a set of Kramers-Kronig (K-K) relations for the corresponding susceptibilities at all orders of nonlinearity. Nonetheless, only a special class of directly observable susceptibilities obey K-K relations. Specific results are provided for the case of arbitrary order harmonic response, which allows for a very comprehensive K-K analysis and the establishment of sum rules connecting the asymptotic behavior of the harmonic generation susceptibility to the short-time response of the perturbed system. These results set in a more general theoretical framework previous findings obtained for optical systems and simple mechanical models, and shed light on the very general impact of considering the principle of causality for testing self-consistency: the described dispersion relations constitute unavoidable benchmarks that any experimental and model generated dataset must obey. The theory exposed in the present paper is dual to the time-dependent theory of perturbations to equilibrium states and to non-equilibrium steady states, and has in principle similar range of applicability and limitations. In order to connect the equilibrium and the non equilibrium steady state case, we show how to rewrite the classical response theory by Kubo so that response functions formally identical to those proposed by Ruelle, apart from the measure involved in the phase space integration, are obtained. These results, taking into account the chaotic hypothesis by Gallavotti and Cohen, might be relevant in several fields, including climate research. In particular, whereas the fluctuation-dissipation theorem does not work for non-equilibrium systems, because of the non-equivalence between internal and external fluctuations, K-K relations might be robust tools for the definition of a self-consistent theory of climate change.

Evidence of dispersion relations for the nonlinear response of the Lorenz 63 system

Along the lines of the nonlinear response theory developed by Ruelle, in a previous paper we have proved under rather general conditions that Kramers-Kronig dispersion relations and sum rules apply for a class of susceptibilities describing at any order of perturbation the response of Axiom A non equilibrium steady state systems to weak monochromatic forcings. We present here the first evidence of the validity of these integral relations for the linear and the second harmonic response for the perturbed Lorenz 63 system, by showing that numerical simulations agree up to high degree of accuracy with the theoretical predictions. Some new theoretical results, showing how to derive asymptotic behaviors and how to obtain recursively harmonic generation susceptibilities for general observables, are also presented. Our findings confirm the conceptual validity of the nonlinear response theory, suggest that the theory can be extended for more general non equilibrium steady state systems, and shed new light on the applicability of very general tools, based only upon the principle of causality, for diagnosing the behavior of perturbed chaotic systems and reconstructing their output signals, in situations where the fluctuation-dissipation relation is not of great help.

Generation of attosecond pulses in molecular nitrogen

We have generated attosecond pulse trains in an ensemble of randomly aligned nitrogen molecules. Measurements of the high-order harmonic relative phases and amplitudes allow us to reconstruct the temporal profile of the attosecond pulses. We show that in the considered spectral range, the latter is very similar to the pulse train generated in argon under the same conditions. We discuss the possible influence of the molecular structure in the generation process, and how it can induce subtle differences on the relative phases.

On the generation mechanisms of short-scale unbalanced modes in rotating two-layer flows with vertical shear

We report on the results of a laboratory investigation using a rotating two-layer annulus experiment, which exhibits both large-scale vortical modes and short-scale divergent modes. A sophisticated visualization method allows us to observe the flow at very high spatial and temporal resolution. The balanced long-wavelength modes appear only when the Froude number is supercritical (i.e. $F\,{>}\,F_\mathrm{critical}\,{\equiv}\, \upi^2/2$), and are therefore consistent with generation by a baroclinic instability. The unbalanced short-wavelength modes appear locally in every single baroclinically unstable flow, providing perhaps the first direct experimental evidence that all evolving vortical flows will tend to emit freely propagating inertia–gravity waves. The short-wavelength modes also appear in certain baroclinically stable flows. We infer the generation mechanisms of the short-scale waves, both for the baro-clinically unstable case in which they co-exist with a large-scale wave, and for the baroclinically stable case in which they exist alone. The two possible mechanisms considered are spontaneous adjustment of the large-scale flow, and Kelvin–Helmholtz shear instability. Short modes in the baroclinically stable regime are generated only when the Richardson number is subcritical (i.e. $\hbox{\it Ri}\,{<}\,\hbox{\it Ri}_\mathrm{critical}\,{\equiv}\, 1$), and are therefore consistent with generation by a Kelvin–Helmholtz instability. We calculate five indicators of short-wave generation in the baroclinically unstable regime, using data from a quasi-geostrophic numerical model of the annulus. There is excellent agreement between the spatial locations of short-wave emission observed in the laboratory, and regions in which the model Lighthill/Ford inertia–gravity wave source term is large. We infer that the short waves in the baroclinically unstable fluid are freely propagating inertia–gravity waves generated by spontaneous adjustment of the large-scale flow.

Spontaneous generation and impact of inertia-gravity waves in a stratified, two-layer shear flow

Inertia-gravity waves exist ubiquitously throughout the stratified parts of the atmosphere and ocean. They are generated by local velocity shears, interactions with topography, and as geostrophic (or spontaneous) adjustment radiation. Relatively little is known about the details of their interaction with the large-scale flow, however. We report on a joint model/laboratory study of a flow in which inertia-gravity waves are generated as spontaneous adjustment radiation by an evolving large-scale mode. We show that their subsequent impact upon the large-scale dynamics is generally small. However, near a potential transition from one large-scale mode to another, in a flow which is simultaneously baroclinically-unstable to more than one mode, the inertia-gravity waves may strongly influence the selection of the mode which actually occurs.

Developing the next-generation climate system models: challenges and achievements

Although climate models have been improving in accuracy and efficiency over the past few decades, it now seems that these incremental improvements may be slowing. As tera/petascale computing becomes massively parallel, our legacy codes are less suitable, and even with the increased resolution that we are now beginning to use, these models cannot represent the multiscale nature of the climate system. This paper argues that it may be time to reconsider the use of adaptive mesh refinement for weather and climate forecasting in order to achieve good scaling and representation of the wide range of spatial scales in the atmosphere and ocean. Furthermore, the challenge of introducing living organisms and human responses into climate system models is only just beginning to be tackled. We do not yet have a clear framework in which to approach the problem, but it is likely to cover such a huge number of different scales and processes that radically different methods may have to be considered. The challenges of multiscale modelling and petascale computing provide an opportunity to consider a fresh approach to numerical modelling of the climate (or Earth) system, which takes advantage of the computational fluid dynamics developments in other fields and brings new perspectives on how to incorporate Earth system processes. This paper reviews some of the current issues in climate (and, by implication, Earth) system modelling, and asks the question whether a new generation of models is needed to tackle these problems.

Questions of Friendship and Degrees of Transnationality among Second-Generation Return Migrants to Barbados

While the academic literature has demonstrated the importance of social networks in relation to the process of migration, investigations have rarely examined in detail the personal-social adjustment issues that migrants and return migrants face. This study examines the context and types of friendship pattern that young return migrants from Britain cultivate in Barbados. The research centres on a wholly under-researched demographic groupyoung return migrants or second-generation Barbadians who have decided to return to the birthplace of their parents. The investigation is based on 51 in-depth interviews carried out with these young returnees to Barbados. Presenting a taxonomy of friendship types, it is argued that, for the 'Bajan-Brits' under study, the cultivation of new friendships is highly problematic. The research identifies what we refer to as the 'insular transnational', the 'we are different' and the 'all-inclusive transnational' friendship types among the young returnees. Our analysis also shows that problems of friendship are highly gendered, with females reporting the most problems due to what is perceived as sexual and workplace competition. It is stressed that these circumstances exemplify the essentially 'hybrid', 'liminal' and 'in-between' positionality of these second-generation migrants within contemporary Barbadian society.

'Black skins-white masks': Postcolonial reflections on 'race', gender and second generation return migration to the Caribbean

This paper illustrates the opportunities afforded by the adoption of postcolonial discourse in development geography, drawing specifically on issues of transnationalism, hybridity and inbetweeness. The utility of such notions and associated approaches is illustrated by the authors' current research on the migration of young, second generation and foreign-born 'Bajan-Brits' to the small Caribbean island nation of Barbados, the homeland of their parents. Focussing on issues of 'race' and gender, the paper examines the experiences of return migration among this cohort from an interpretative perspective framed within postcolonial discourse. It argues that notwithstanding the considerable sociocultural problems of adjustment encountered, these Bajan-Brit 'returnees' may be seen as occupying positions of relative economic privilege. Theirs is a liminal space derived by virtue of having been born and/or raised in the UK and being of the black 'race'. Accordingly, they are demonstrated to be both advantaged and disadvantaged; both transnational and national; and black but, in some senses, symbolically white.

Quality of Life Issues and Second-Generation Migration: the Case of 'Bajan-Brit Returnees'

This paper forms part of research that is investigating the migration of young Bajan-Brits to Barbados. Specifically, it explores the role of quality of life issues in the decision-making processes of young Bajan-Brits as they negotiate their 'return' to Barbados. The research, based on 51 in-depth qualitative interviews conducted with an under-researched cohort of young Bajan-Brits living in Barbados, argues from a 'lure of home' conceptualisation that the return of young Bajan-Brits to Barbados can best be understood from the context of a search for a better quality of life in the face of social and economic disenfranchisement in the UK context. Subsequently, the paper examines the extent to which the quality of life factors which formed the basis of return to Barbados have in fact been realised on the part of young Bajan-Brits in their adjustment to life in Barbados. The paper ultimately argues that despite problems of adjustment, young Bajan-Brits have generally been successful in actualising a better quality of life in Barbados. Copyright (C) 2009 John Wiley & Sons, Ltd.