323 resultados para Failed State

em Queensland University of Technology - ePrints Archive


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The last decade has seen an emerging consensus that the rule of law is critical in both domestic and international affairs. ‘Failedstates generate important issues for both the rule of law and, importantly, for their intersection or interaction. A ‘failedstate almost inevitably involves a breakdown of the domestic rule of law. When international intervention occurs, it raises concerns over substantive issues. Among these is the application of international law and international norms, including among other, the conventions and treaties, the responsibility to protect and protection of civilians. Where international missions seek to assist the people of ‘failedstates in rebuilding their nations, establishing the rule of law is often the primary or initial pursuit. Any such international assistance/intervention is more effective if it is clearly subject to the rule of law and provides an exemplar/demonstration of how power should be exercised

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Campaigning in Australian election campaigns at local, state, and federal levels is fundamentally affected by the fact that voting is compulsory in Australia, with citizens who are found to have failed to cast their vote subject to fines. This means that - contrary to the situation in most other nations – elections are decided not by which candidate or party has managed to encourage the largest number of nominal supporters to make the effort to cast their vote, but by some 10-20% of genuine ‘swinging voters’ who change their party preferences from one election to the next. Political campaigning is thus aimed less at existing party supporters (so-called ‘rusted on’ voters whose continued support for the party is essentially taken for granted) than at this genuinely undecided middle of the electorate. Over the past decades, this has resulted in a comparatively timid, vague campaigning style from both major party blocs (the progressive Australian Labor Party [ALP] and the conservative Coalition of the Liberal and National Parties [L/NP]). Election commitments that run the risk of being seen as too partisan and ideological are avoided as they could scare away swinging voters, and recent elections have been fought as much (or more) on the basis of party leaders’ perceived personas as they have on stated policies, even though Australia uses a parliamentary system in which the Prime Minister and state Premiers are elected by their party room rather than directly by voters. At the same time, this perceived lack of distinctiveness in policies between the major parties has also enabled the emergence of new, smaller parties which (under Australia’s Westminster-derived political system) have no hope of gaining a parliamentary majority but could, in a close election, come to hold the balance of power and thus exert disproportionate influence on a government which relies on their support.

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We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.