Competing C–Br and C–C Bond Fission Following 1[n(O),π∗(C=O)] Excitation in Bromoacetone: Conformation Dependence of Nonadiabaticity at a Conical Intersection

These experiments investigate the competition between C-C and C-Br bond fission in bromoacetone excited in the (1)[n(O),pi(*)(C=O)] absorption, elucidating the role of molecular conformation in influencing the probability of adiabatically traversing the conical intersection along the C-C fission reaction coordinate. In the first part of the paper, measurement of the photofragment velocity and angular distributions with a crossed laser-molecular beam time-of-flight technique identifies the primary photofragmentation channels at 308 nm. The time-of-flight spectra evidence two dissociation channels, C-Br fission and fission of one of the two C-C bonds, BrH2C-COCH3. The distribution of relative kinetic energies imparted to the C-Br fission and C-C fission fragments show dissociation is not occurring via internal conversion to the ground electronic state and allow us to identify these channels in the closely related systems of bromoacetyl- and bromopropionyl chloride. In the second part of the work we focus on the marked conformation dependence to the branching between C-C fission and C-Br fission. Photofragment angular distribution measurements show that C-Br fission occurs primarily from the minor, anti, conformer, giving a beta of 0.8, so C-C fission must dominate the competition in the gauche conformer. Noting that the dynamics of these two bond fission pathways are expected to be strongly influenced by nonadiabatic recrossing of the reaction barriers, we investigate the possible mechanisms for the conformation dependence of the nonadiabatic recrossing with low-level ab initio electronic structure calculations on the C-Br reaction coordinate and qualitative consideration of the conical intersection along the C-C reaction coordinate. The resulting model proposes that C-C bond fission,cannot compete with C-Br fission in the anti conformer because the dissociation samples regions of the phase space near the conical intersection along the CC fission reaction coordinate, where nonadiabaticity inhibits C-C fission, while from the gauche conformer C-C fission can proceed more adiabatically and dominate C-Br fission. A final experiment confirms that the branching ratio changes with the relative conformer populations in accord with this model

Use of the breeding technique to estimate the structure of the analysis 'errors of the day'

A 3D-variational data assimilation scheme for a quasi-geostrophic channel model (Morss, 1998) is used to study the structure of the background error and its relationship to the corresponding bred vectors. The "true" evolution of the model atmosphere is defined by an integration of the model and "rawinsonde observations" are simulated by randomly perturbing the true state at fixed locations. Case studies using different observational densities are considered to compare the evolution of the Bred Vectors to the spatial structure of the background error. In addition, the bred vector dimension (BV-dimension), defined by Patil et al. (2001) is applied to the bred vectors. It is found that after 3-5 days the bred vectors develop well organized structures which are very similar for the two different norms (enstrophy and streamfunction) considered in this paper. When 10 surrogate bred vectors (corresponding to different days from that of the background error) are used to describe the local patterns of the background error, the explained variance is quite high, about 85-88%, indicating that the statistical average properties of the bred vectors represent well those of the background error. However, a subspace of 10 bred vectors corresponding to the time of the background error increased the percentage of explained variance to 96-98%, with the largest percentage when the background errors are large. These results suggest that a statistical basis of bred vectors collected over time can be used to create an effective constant background error covariance for data assimilation with 3D-Var. Including the "errors of the day" through the use of bred vectors corresponding to the background forecast time can bring an additional significant improvement

Checking the list: Can a model of Down syndrome help us explore the intellectual accessibility of Heritage sites?

There is currently a lack of provision for, and research into, the intellectual accessibility of heritage sites. This paper explores some possible ways forward. It examines recent research with people described as having Down syndrome and uses the syndrome's identified characteristics to create good practice guidelines. It assesses these guidelines against an audio tour written for people with learning difficulties. In conclusion, the paper suggests that drawing upon a generalised model of Down syndrome and these good practice guidelines will allow sites to identify some potential barriers and enablers to intellectual accessibility, but that fully to appreciate the effectiveness of their provision they must still institute site?specific research by people with learning difficulties

Anarchism, individualism and communism: William Morris's critique of anarcho-communism

This collection of essays, showing how the boundaries between Marxism and anarchism have been more porous and fruitful than is conventionally recognised, charts a history of radical socialist collaborations from the late 19th ..

Schumpeter: Theorist of the Avant-Garde

This paper argues that Schumpeter’s 1911 edition of ‘Theory of Economic Development’ can be fruitfully read as a theory of the avant-garde, in line with such theories developed by artistic avant-garde around the same time, in particular by the Italian Futurists. In particular it will show that both Schumpeter and other avant-garde theorists sought to break with past (1), identify an avant-garde who could force that break (2), find new ways to represent the dynamic world (3), embrace the new and dynamic (4) and promote a perpetual dynamic process, instead of a specific end-state or utopia (5). This new reading helps us to understand the cultural meaning of this seminal text in economics. Secondly it greatly facilitates our understanding of the differences with the later interwar German edition and English edition, which were more cautious in their embrace of the new, less focused on the individual qualities of the entrepreneur and placed more emphasis on historical continuity. Thirdly this reading suggests a different reason for the bifurcation between Schumpeter and the rest of the Austrian school of economics. Traditionally this split is explained by Schumpeter’s affinities with the Lausanne School, this paper instead suggests that the crucial break between Schumpeter on the one hand and Böhm-Bawerk, Wieser and later members of the Austrian School on the other hand is their theory of and attitude toward social change

Human(e) rights and the cosmopolitan imagination: questions of human dignity and cultural identity

Here I seek to explore the cosmopolitan foundations of the idea of human rights. The argument begins by considering the popularity of the idea of human rights in a globalized and fast-moving commodified and digital culture. At this point I consider whether the idea of human rights might be considered to be a modern utopia similar to the role that art and nature played in the Romantic movements of the 19th century. Further, I defend human rights against those who simply see it as a form of neoliberalism or as largely ineffective against the power of the state. At this point I investigate some of the Durkheimian work within cultural sociology that has sought to investigate human rights as a form of moral community. The main problem with this view is that it has little to say about human freedom. However, viewed through a cultural lens, the global spread of human rights is connected to the idea of human dignity. While there is never likely to be a global consensus on this term, it does retain an important philosophical anchoring in Kantian ideas. More recently this debate has been revived by the critical reception of the work of Agamben and his idea of ‘bare life’. If human rights can indeed be connected to the struggle for a dignified and meaningful life, then the idea of ‘bare life’ remains an important conceptual advance. However, by considering the work and legacy of Du Bois, Gilroy and others, we can also see how the term dignity might take on other meanings in different settings. Finally, I argue that the idea of dignity and human rights could yet provide an important focus for resistance against the imperatives of capital and state in these neoliberal times

Nature of the 5f states in actinide metals

Actinide elements produce a plethora of interesting physical behaviors due to the 5f states. This review compiles and analyzes progress in understanding of the electronic and magnetic structure of the 5f states in actinide metals. Particular interest is given to electron energy-loss spectroscopy and many-electron atomic spectral calculations, since there is now an appreciable library of core d -> valence f transitions for Th, U, Np, Pu, Am, and Cm. These results are interwoven and discussed against published experimental data, such as x-ray photoemission and absorption spectroscopy, transport measurements, and electron, x-ray, and neutron diffraction, as well as theoretical results, such as density-functional theory and dynamical mean-field theory.Comment: 136 pages in Word format, 29 Figures; Accepted to Reviews of Modern Physic

Reflection Asymmetric Shapes in Nuclei

Experimental data show that there is no even-even nucleus with a reflection asymmetric shape in its ground state. Maximum octupole- octupole correlations occur in nuclei in the mass 224 (N{approximately}134, Z{approximately}88) region. Parity doublets, which are the characteristic signature of octupole deformation, have been observed in several odd mass Ra, Ac and Pa nuclei. Intertwined negative and positive parity levels have been observed in several even-even Ra and Th nuclei above spin {approximately}8{Dirac h}. In both cases, the opposite parity states are connected by fast El transitions. In some medium-mass nuclei intertwined negative and positive parity levels have also been observed above spin {approximately}7{Dirac h}. The nuclei which exhibit octupole deformation in this mass region are {sup 144}Ba, {sup 146}Ba and {sub 146}Ce; {sup 142}Ba, {sup 148}Ce, {sup 150}Ce and {sup 142}Xe do not show these characteristics. No case of parity doublet has been observed in the mass 144 region. 32 refs., 16 figs., 1 tab

Donors, Aid and Taxation in Developing Countries: An Overview

Recent years have witnessed rapidly growing donor interest in tax issues in the developing world. This reflects a concern with revenue collection to finance public spending, but also recognition of the centrality of taxation to growth, redistribution and broader state-building and governance goals. Against this backdrop, this paper identifies a series of key issues that demand attention if donors are to improve the quality of their support for tax reform. The focus is not, primarily, on the technical design of tax interventions, but, instead, on seven ‘big picture’ considerations for the design of donor programmes: (a) supporting local leadership of reform efforts; (b) incorporating more systematic political economy analysis into the design and implementation of reform programmes; (c) designing tax reform programmes that seek to foster broader linkages between taxation, state-building and governance; (d) paying careful attention to the complexity of the relationship between aid and tax effort; (e) better designing tax-related conditionality, particularly by developing a more nuanced set of performance indicators; (f) ensuring the effective coordination of donor interventions; and (g) paying greater attention to the international policy context, and particularly the role of tax exemptions for donor projects, tax havens and tax evasion by multinational corporations (MNCs) in undermining developing country tax systems.DfI