Estimation of electronic coupling in π -stacked donor-bridge-acceptor systems: correction of the two-state model

Comparison of donor-acceptor electronic couplings calculated within two-state and three-state models suggests that the two-state treatment can provide unreliable estimates of Vda because of neglecting the multistate effects. We show that in most cases accurate values of the electronic coupling in a π stack, where donor and acceptor are separated by a bridging unit, can be obtained as Ṽ da = (E2 - E1) μ12 Rda + (2 E3 - E1 - E2) 2 μ13 μ23 Rda2, where E1, E2, and E3 are adiabatic energies of the ground, charge-transfer, and bridge states, respectively, μij is the transition dipole moments between the states i and j, and Rda is the distance between the planes of donor and acceptor. In this expression based on the generalized Mulliken-Hush approach, the first term corresponds to the coupling derived within a two-state model, whereas the second term is the superexchange correction accounting for the bridge effect. The formula is extended to bridges consisting of several subunits. The influence of the donor-acceptor energy mismatch on the excess charge distribution, adiabatic dipole and transition moments, and electronic couplings is examined. A diagnostic is developed to determine whether the two-state approach can be applied. Based on numerical results, we showed that the superexchange correction considerably improves estimates of the donor-acceptor coupling derived within a two-state approach. In most cases when the two-state scheme fails, the formula gives reliable results which are in good agreement (within 5%) with the data of the three-state generalized Mulliken-Hush model

The role of the basic state in the ENSO-monsoon relationship and implications for predictability

The impact of systematic model errors on a coupled simulation of the Asian Summer monsoon and its interannual variability is studied. Although the mean monsoon climate is reasonably well captured, systematic errors in the equatorial Pacific mean that the monsoon-ENSO teleconnection is rather poorly represented in the GCM. A system of ocean-surface heat flux adjustments is implemented in the tropical Pacific and Indian Oceans in order to reduce the systematic biases. In this version of the GCM, the monsoon-ENSO teleconnection is better simulated, particularly the lag-lead relationships in which weak monsoons precede the peak of El Nino. In part this is related to changes in the characteristics of El Nino, which has a more realistic evolution in its developing phase. A stronger ENSO amplitude in the new model version also feeds back to further strengthen the teleconnection. These results have important implications for the use of coupled models for seasonal prediction of systems such as the monsoon, and suggest that some form of flux correction may have significant benefits where model systematic error compromises important teleconnections and modes of interannual variability.

On the use of headline indices to link environmental quality and income at the level of the nation state

This paper deconstructs the relationship between the Environmental Sustainability Index (ESI) and national income. The ESI attempts to provide a single figure which encapsulates environmental sustainability' for each country included in the analysis, and this allied with a 'league table' format so as to name and shame bad performers, has resulted in widespread reporting within the popular presses of a number of countries. In essence, the higher the value of the ESI then the more 'environmentally sustainable' a country is deemed to be. A logical progression beyond the use of the ESI to publicise environmental sustainability is its use within a more analytical context. Thus an index designed to simplify in order to have an impact on policy is used to try and understand causes of good and bad performance in environmental sustainability. For example the creators of the ESI claim that ESI is related to GDP/capita (adjusted for Purchasing Power Parity) such that the ESI increases linearly with wealth. While this may in a sense be a comforting picture, do the variables within the ESI allow for alternatives to the story, and if they do then what are the repercussions for those producing such indices for broad consumption amongst the policy makers, mangers, the press, etc.? The latter point is especially important given the appetite for such indices amongst non-specialists, and for all their weaknesses the ESI and other such aggregated indices will not go away. (C) 2007 Elsevier Ltd. All rights reserved.

Variation of the mixing state of Saharan dust particles with atmospheric transport

Mineral dust is an important aerosol species in the Earth’s atmosphere and has a major source within North Africa, of which the Sahara forms the major part. Aerosol Time of Flight Mass Spectrometry (ATOFMS) is first used to determine the mixing state of dust particles collected from the land surface in the Saharan region, showing low abundance of species such as nitrate and sulphate internally mixed with the dust mineral matrix. These data are then compared with the ATOFMS single particle mass spectra of Saharan dust particles detected in the marine atmosphere in the vicinity of the Cape Verde islands, which are further compared with those from particles with longer atmospheric residence sampled at a coastal station at Mace Head, Ireland. Saharan dust particles collected near the Cape Verde Islands showed increased internally mixed nitrate but no sulphate, whilst Saharan dust particles collected on the coast of Ireland showed a very high degree of internally mixed secondary species including nitrate, sulphate and methanesulphonate. This uptake of secondary species will change the pH and hygroscopic properties of the aerosol dust and thus can influence the budgets of other reactive gases, as well as influencing the radiative properties of the particles and the availability of metals for dissolution.

Exploring the construction of social class in educational discourse: the rational order of the nation state versus global uncertainties

This article aims to create intellectual space in which issues of social inequality and education can be analyzed and discussed in relation to the multifaceted and multi-levelled complexities of the modern world. It is divided into three sections. Section One locates the concept of social class in the context of the modern nation state during the period after the Second World War. Focusing particularly on the impact of 'Fordism' on social organization and cultural relations, it revisits the articulation of social justice issues in the United Kingdom, and the structures put into place at the time to alleviate educational and social inequalities. Section Two problematizes the traditional concept of social class in relation to economic, technological and sociocultural changes that have taken place around the world since the mid-1980s. In particular, it charts some of the changes to the international labour market and global patterns of consumption, and their collective impact on the re-constitution of class boundaries in 'developed countries'. This is juxtaposed with some of the major social effects of neo-classical economic policies in recent years on the sociocultural base in developing countries. It discusses some of the ways these inequalities are reflected in education. Section Three explores tensions between the educational ideals of the 'knowledge economy' and the discursive range of social inequalities that are emerging within and beyond the nation state. Drawing on key motifs identified throughout, the article concludes with a reassessment of the concept of social class within the global cultural economy. This is discussed in relation to some of the major equity and human rights issues in education today.

Exploring the construction of social class in educational discourse: the rational order of the nation state vs. global uncertainties

This article aims to create intellectual space in which issues of social inequality and education can be analyzed and discussed in relation to the multifaceted and multi-levelled complexities of the modern world. It is divided into three sections. Section One locates the concept of social class in the context of the modern nation state during the period after the Second World War. Focusing particularly on the impact of ‘Fordism’ on social organization and cultural relations, it revisits the articulation of social justice issues in the United Kingdom, and the structures put into place at the time to alleviate educational and social inequalities. Section Two problematizes the traditional concept of social class in relation to economic, technological and sociocultural changes that have taken place around the world since the mid-1980s. In particular, it charts some of the changes to the international labour market and global patterns of consumption, and their collective impact on the re-constitution of class boundaries in ‘developed countries’. This is juxtaposed with some of the major social effects of neo-classical economic policies in recent years on the sociocultural base in developing countries. It discusses some of the ways these inequalities are reflected in education. Section Three explores tensions between the educational ideals of the ‘knowledge economy’ and the discursive range of social inequalities that are emerging within and beyond the nation state. Drawing on key motifs identified throughout, the article concludes with a reassessment of the concept of social class within the global cultural economy. This is discussed in relation to some of the major equity and human rights issues in education today.

Conditioning and preconditioning of the optimal state estimation problem

Optimal state estimation is a method that requires minimising a weighted, nonlinear, least-squares objective function in order to obtain the best estimate of the current state of a dynamical system. Often the minimisation is non-trivial due to the large scale of the problem, the relative sparsity of the observations and the nonlinearity of the objective function. To simplify the problem the solution is often found via a sequence of linearised objective functions. The condition number of the Hessian of the linearised problem is an important indicator of the convergence rate of the minimisation and the expected accuracy of the solution. In the standard formulation the convergence is slow, indicating an ill-conditioned objective function. A transformation to different variables is often used to ameliorate the conditioning of the Hessian by changing, or preconditioning, the Hessian. There is only sparse information in the literature for describing the causes of ill-conditioning of the optimal state estimation problem and explaining the effect of preconditioning on the condition number. This paper derives descriptive theoretical bounds on the condition number of both the unpreconditioned and preconditioned system in order to better understand the conditioning of the problem. We use these bounds to explain why the standard objective function is often ill-conditioned and why a standard preconditioning reduces the condition number. We also use the bounds on the preconditioned Hessian to understand the main factors that affect the conditioning of the system. We illustrate the results with simple numerical experiments.

Three-body model of the final state interaction in heavy meson decay

We develop a relativistic three-body model for the final state interaction in D(+) -> K(-) pi(+) pi(+) decay based on the ladder approximation of the Bethe-Salpeter equation. The decay amplitude has the standard two-meson resonant transition matrix modulated by a spectator amplitude that carries a fully interacting three-body contribution and a smooth background term from the partonic amplitude. Our calculations are compared with D decay data.

Solutions of the bound-state Faddeev-Yakubovsky equations in three dimensions by using NN and 3N potential models

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dehydration and volatilization non isothermic kinetic of the solid state aluminium 8-hydroxyquinolinate

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

RAPD analysis of the sexual state and sterile mycelium of the fungus cultivated by the leaf-cutting ant Acromyrmex hispidus fallax

That the symbiotic fungus of leaf-cutting ants only occasionally produces the sexual phase makes their identification confusing. This has occurred so rarely, either in laboratory nests, or in unbalanced field nests. that the possibility of contamination of the fungal garden by other fungi cannot be disregarded. In this paper we describe the formation of several basidiomata in a healthy and free-living nest of the leaf-cutting ant Acromyrmex hispidus fallax. The cultivation in vitro of the sterile mycelia (isolated from the fungal garden) with their typical inflated tips, and the similarity of both forms confirmed by RAPD analysis of their genomic DNA. The fungus was identified as Leucoagaricus gongylophorus.