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.

An investigation of nucleation events in a coastal urban environment in the southern hemisphere

The occurrence of and conditions favourable to nucleation were investigated at an industrial and commercial coastal location in Brisbane, Australia during five different campaigns covering a total period of 13 months. To identify potential nucleation events, the difference in number concentration in the size range 14-30 nm (N14-30) between consecutive observations was calculated using first-order differencing. The data showed that nucleation events were a rare occurrence, and that in the absence of nucleation the particle number was dominated by particles in the range 30-300 nm. In many instances, total particle concentration declined during nucleation. There was no clear pattern in change in NO and NO2 concentrations during the events. SO2 concentration, in the majority of cases, declined during nucleation but there were exceptions. Most events took place in summer, followed by winter and then spring, and no events were observed for the autumn campaigns. The events were associated with sea breeze and long-range transport. Roadside emissions, in contrast, did not contribute to nucleation, probably due to the predominance of particles in the range 50-100 nm associated with these emissions.

Electronic states of trans-polyacetylene, poly(p-phenylene vinylene) and sp-hybridised carbon species in amorphous hydrogenated carbon probed by resonant Raman scattering

Inclusions of sp-hybridised, trans-polyacetylene [trans-(CH)x] and poly(p-phenylene vinylene) (PPV) chains are revealed using resonant Raman scattering (RRS) investigation of amorphous hydrogenated carbon (a-C:H) films in the near IR – UV range. The RRS spectra of trans-(CH)x core Ag modes and the PPV CC-H phenylene mode are found to transform and disperse as the laser excitation energy ћωL is increased from near IR through visible to UV, whereas sp-bonded inclusions only become evident in UV. This is attributed to ћωL probing of trans-(CH)x chain inhomogeneity and the distribution of chains with varying conjugation length; for PPV to the resonant probing of phelynene ring disorder; and for sp segments, to ћωL probing of a local band gap of end-terminated polyynes. The IR spectra analysis confirmed the presence of sp, trans-(CH)x and PPV inclusions. The obtained RRS results for a-C:H denote differentiation between the core Ag trans-(CH)x modes and the PPV phenylene mode. Furthermore, it was found that at various laser excitation energies the changes in Raman spectra features for trans-(CH)x segments included in an amorphous carbon matrix are the same as in bulk trans-polyacetylene. The latter finding can be used to facilitate identification of trans-(CH)x in the spectra of complex carbonaceous materials.

Electronic workplace surveillance and employee privacy : a comparative analysis of privacy protection in Australia and the United States

More than a century ago in their definitive work “The Right to Privacy” Samuel D. Warren and Louis D. Brandeis highlighted the challenges posed to individual privacy by advancing technology. Today’s workplace is characterised by its reliance on computer technology, particularly the use of email and the Internet to perform critical business functions. Increasingly these and other workplace activities are the focus of monitoring by employers. There is little formal regulation of electronic monitoring in Australian or United States workplaces. Without reasonable limits or controls, this has the potential to adversely affect employees’ privacy rights. Australia has a history of legislating to protect privacy rights, whereas the United States has relied on a combination of constitutional guarantees, federal and state statutes, and the common law. This thesis examines a number of existing and proposed statutory and other workplace privacy laws in Australia and the United States. The analysis demonstrates that existing measures fail to adequately regulate monitoring or provide employees with suitable remedies where unjustifiable intrusions occur. The thesis ultimately supports the view that enacting uniform legislation at the national level provides a more effective and comprehensive solution for both employers and employees. Chapter One provides a general introduction and briefly discusses issues relevant to electronic monitoring in the workplace. Chapter Two contains an overview of privacy law as it relates to electronic monitoring in Australian and United States workplaces. In Chapter Three there is an examination of the complaint process and remedies available to a hypothetical employee (Mary) who is concerned about protecting her privacy rights at work. Chapter Four provides an analysis of the major themes emerging from the research, and also discusses the draft national uniform legislation. Chapter Five details the proposed legislation in the form of the Workplace Surveillance and Monitoring Act, and Chapter Six contains the conclusion.

Procurement selection in the public sector : a tale of two states.

The decision as to which procurement system to adopt is a complex and challenging task for clients of construction projects. Despite a plethora of tools and techniques available for selecting a procurement method, clients are still uncertain about what method to adopt for a given construction project to achieve success. This paper examines ‘how and why’ procurement methods are selected by public sector clients in Queensland (QLD) and Western Australia (WA). Findings from workshops with senior managers in procurement selection revealed that traditional lump sum methods (TLS) are preferred even though alternative forms could be better suited for a given project. Participants of the workshops agreed that alternative procurement forms should be considered for projects but an embedded culture of uncertainty avoidance meant the selection of TLS methods. It was perceived that only a limited number of contractors operating in the marketplace have the resources and experience to deliver projects using the non-traditional methods.

Driving and licensing experiences of learner drivers in two Australian states prior to major changes in the licensing laws

The learner licence is an important component of the graduated driver licensing system. This research describes the driving and licensing experiences of learner drivers in Queensland and New South Wales licensed prior to the changes made to the system in mid-2007. The sample consisted of 392 participants who completed a telephone interview just after they obtained their provisional licence. The results suggest that learner drivers in the two states had many similar experiences when they were obtaining a learner licence. However, once a learner licence was obtained, there were differences in the amount of practice, the supervisor learners practised with, the type of vehicle they used and the amount of unlicensed driving. This paper provides important baseline descriptive data that can be used to measure the impact of the changes that were introduced to the learner licence phase in mid-2007 in both of these states.

Conference Report of the First Meeting of the Native American and Indigenous Studies Association, 21-23 May 2009, Department of American Indian Studies, University of Minneapolis, Minesota, United States of America

Report provided back by Bronwyn Fredericks on her participation at the First Native American and Indigenous Studies Association Meeting held 21-23 May 2009 in Minnesota, United States of America.

A review of the video games industry in the United States

With increasing revenues for video game manufacturers, higher software sales and a more diverse audience, the video games industry has been experiencing strong and rapid growth in recent times, rivalling other forms of entertainment. As a result, games have begun to attract the attention of marketing practitioners who are finding it increasingly difficult to attract consumer attention, and are seeking alternative media for marketing communications. This paper provides a review of the video games industry in the United States and raises the question as to whether games are a viable new medium for marketing messages. Areas for research are identified.

A comparison of farmland returns in Australia, Canada, New Zealand and United States

Rural land is still a major property asset class and rural commodity production is an important domestic and export market in all economies. This paper carries out a comprehensive analysis of both rural production and land prices in four major rural production countries. The study compares rural property values in Unites States, Canada, Australia and New Zealand over a period 1990 to 2005 and analyzes and compares the capital return and total return performance for rural land in these four countries. The analysis allows a comparison of farm land returns for both a subsidised and non-subsidised farming policy to determine if levels of farm support result in variations in farm profitability and therefore farm land values.

Southern theory and its dynamics for postcolonial education

This paper discusses how the exploration of social texts and historical contexts from the global 'South', as put forward in Raewyn Connell's study 'Southern Theory' (2007), can improve the theoretical tools used in postcolonial education analysis. Connell analyses a selection of excellent and compelling social theory texts written by scholars in Africa, India, Iran, Latin America and Australia to show how they challenge and counter the silences, distortions and plain lies of dominant Western social theory. These texts of the global South do not mince words in laying bare the role of the institutions and elites of the West in the destruction, dispossession, and bloodshed involved in creating the world in which we live, and in perpetuating its catastrophes. The texts also reveal intense debates between scholars over their conceptualisations of local, national and global society. My paper argues that this kind of work is of vital importance to postcolonial studies in education. It helps education scholars to uncover the problematic assumptions and distortions of dominant education thought, and understand different ways of seeing. Postcolonial educators could use this to help both students and teacher unlearn many of our taught perceptions of the world, whether in the global North or the global South. Developing a countervailing social theory in education would sharpen our questioning of the structures of schooling as they relate to society, and tease out new dimensions of postcolonial leadership for education.