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.

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.

Buying a sponsor’s brand : the role of affective commitment to the sponsored team

Sponsorship is increasingly important in a firm’s communication mix. Research to date has focused on the impact of sponsorship on brand awareness and its subsequent consequences for image congruency and consumer attitudes towards sponsors’ brands. A lesser studied area is the effect of sponsorship on consumers’ purchase intentions and behaviours. We argue that existing models of sponsorship driven purchase behaviour fail to account for affective commitment, which mediates relationship between affiliation with the team and social identification with the team. We propose a modified framework describing the effect of sponsorship on purchase intentions in the context of low and high performing sports teams. The framework is tested using structural equations modelling; employing PLS estimation and data collected via online survey of AFL chat room participants. Results confirm the role of affective commitment in sport sponsorship purchase intentions and indicate that team success has a significant influence on fans’ purchase behaviours.

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.

¡Latin jazz! : a syncretic journey from Spain, Cuba, the United States and back

The creative work, ¡Latin Jazz! is a 50 minute radio documentary to be broadcast on ABC Classic FM. It looks at the evolution of Latin jazz from Spain, Cuba and the United States. It examines the social effects on the style and specifically on the syncretic movement between the countries. The documentary traces my travel to Madrid, Spain and looks at Latin jazz through a deconstruction of the style, musical examples and interviews with prominent artists. Artists interviewed were Chano Domínguez, a Spanish flamenco jazz pianist, Bobby Martínez an American saxophonist, Alain Pérez a Cuban bassist and Pepe Rivero a Cuban pianist. The exegesis supports the radio documentary by examining the style in more depth, and is broken into three main sections. First it traces the historical relationship that occurred through the Ida y Vuelta (To and Fro), the similarities and influences through the habanera, the decíma and the religion of Santería. This is followed by specific musical elements within Latin jazz such as instrumentation, clave, harmony and improvisation, whilst the third section looks at the influences of the new syncretic movement back to Spain.

Employee engagement : the development of a three dimensional model of engagement; and an exploration of its relationship with affective leader behaviours

This study was designed to examine affective leader behaviours, and their impact on cognitive, affective and behavioural engagement. Researchers (e.g., Cropanzano & Mitchell, 2005; Moorman et al., 1998) have called for more research to be directed toward modelling and testing sets of relationships which better approximate the complexity associated with contemporary organisational experience. This research has attempted to do this by clarifying and defining the construct of engagement, and then by examining how each of the engagement dimensions are impacted by affective leader behaviours. Specifically, a model was tested that identifies leader behaviour antecedents of cognitive, affective and behavioural engagement. Data was collected from five public-sector organisations. Structural equation modelling was used to identify the relationships between the engagement dimensions and leader behaviours. The results suggested that affective leader behaviours had a substantial direct impact on cognitive engagement, which in turn influenced affective engagement, which then influenced intent to stay and extra-role performance. The results indicated a directional process for engagement, but particularly highlighted the significant impact of affective leader behaviours as an antecedent to engagement. In general terms, the findings will provide a platform from which to develop a robust measure of engagement, and will be helpful to human resource practitioners interested in understanding the directional process of engagement and the importance of affective leadership as an antecedent to engagement.