Introduction

This paper conceptualises think tanks and edu-businesses in relation to education policy work in the Australian polity. It situates the enhanced influence of both in relation to the restructured state, which has lost some key capacities in relation to the generation of research and ideas for policy. This restructuring has been strongly influenced by the techniques of new public management, the auditing of education through national and international testing and new forms of network governance, which have opened up spaces for the increased influence of think tanks and edu-businesses across the policy cycle in education. We see here the workings of a ‘polycentric state’. The paper also considers changing concepts of ‘evidence’, ‘expertise’ and ‘influence’ in respect of the involvement of think tanks and edu-businesses in circulating policy ideas and affecting policy development in Australian education. This introduction to this special issue of The Australian Educational Researcher serves as a provocation to further research on this new policy scenario.

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.