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.

Using performance measurement models for benefit realization with enterprise systems: The Queensland Government approach (Case Study)

A range of influences, technical and organizational, has encouraged the wide spread adaption of Enterprise Systems (ES). Nevertheless, there is a growing consensus that Enterprise Systems have in the many cases failed to provide the expected benefits to organizations. This paper presents ongoing research, which analyzes the benefits realization approach of the Queensland Government. This approach applies a modified Balance Scorecard. First, history and background of Queensland Government’s Enterprise Systems initiative is introduced. Second, the most common reasons for ES under performance are related. Third, relevant performance measurement models and the Balanced Scorecard in particular are discussed. Finally, the Queensland Government initiative is evaluated in light of this overview of current work in the area. In the current and future work, the authors aim to use their active involvement in Queensland Government’s benefits realization initiative for an Action Research based project investigating the appropriateness of the Balanced Scorecard for the purposes of Enterprise Systems benefits realization.