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.