Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

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.

Queensland's Smart State Initiative : a successful knowledge based urban development strategy

The chapter will set out to explain the KBUD and urban policy making processes in Queensland, Australia. This chapter will draw on providing a clear understanding on policy frameworks and relevant ICT applications of the Queensland ‘Smart State��� experience. The chapter is consisted of six sections. The first section following the introduction provides background information. The second section focuses on the KBUD processes in Queensland. The third section offers a comprehensive analysis of the ‘Queensland Smart State��� initiative, and it also identifies actors and goals of the agenda of Smart State experience. The fourth section reviews knowledge based development and ICT applications and policies of the Queensland Smart State and Brisbane Smart City experiences, and their impacts on Brisbane’s successful KBUD. The fifth section discusses knowledge hubs and ICT developments within the Brisbane metropolitan area. Then the chapter concludes with future trends and conclusion sections.

ICT integration and teachers' confidence in using ICT for teaching and learning in Queensland state schools

Information and communication technology (ICT) curriculum integration is the apparent goal of an extensive array of educational initiatives in all Australian states and territories. However, ICT curriculum integration is neither value neutral nor universally understood. The literature indicates the complexity of rationales and terminology that underwrite various initiatives; various dimensions and stages of integration; inherent methodological difficulties; obstacles to integration; and significant issues relating to teacher professional development and ICT competencies (Jamieson-Proctor, Watson, & Finger, 2003). This paper investigates the overarching question: Are ICT integration initiatives making a significant impact on teaching and learning in Queensland state schools? It reports the results from a teacher survey that measures the quantity and quality of student use of ICT. Results from 929 teachers across all year levels and from 38 Queensland state schools indicate that female teachers (73% of the full time teachers in Queensland state schools in 2005) are significantly less confident than their male counterparts in using ICT with students for teaching and learning, and there is evidence of significant resistance to using ICT to align curriculum with new times and new technologies. This result supports the hypothesis that current initiatives with ICT are having uneven and less than the desired results system wide. These results require further urgent investigation in order to address the factors that currently constrain the use of ICT for teaching and learning.

Fear, trust and Aborigines : The historical experience of state institutions and current encounters in the health system

Troubled dynamics between residents of an Aboriginal town in Queensland and the local health system were established during colonisation and consolidated during those periods of Australian history where the policies of 'protection' (segregation), integration and then assimilation held sway. The status of Aboriginal health is, in part, related to interactions between the residents' current and historical experiences of the health and criminal justice systems as together these agencies used medical and moral policing to legitimate dispossession, marginalisation, institutionalisation and control of the residents. The punitive regulations and ethnocentric strategies used by these institutions are within the living memory of many of the residents or in the published accounts of preceding generations. This paper explores current residents' memories and experiences.

Service analysis : A critical assessment of the state of the art

The service-orientation paradigm has not only become prevalent in the software systems domain in recent years, but is also increasingly applied on the business level to restructure organisational capabilities. In this paper, we present the results of an extensive literature review of 30 approaches related to service identification and analysis for both domains. Based on the consolidation of a superset of comparison criteria for service-oriented methodologies found in related literature, we compare and evaluate the different characteristics of service engineering methods with a focus on service analysis. Although a close business and IT alignment is regarded as one of the core beneficial promises of service-orientation, our analysis suggests that there is a lack of unified, comprehensive methodology for service identification and analysis integrating and addressing both domains. Thus, we discuss how our results can inform directions for future research in this area.