Trapping phosphorus (III) into polyoxometalates: synthesis, characterisation and electronic behaviour study

The introduction of electronically-active heteroanions into polyoxometalates (POMs) is one of the emerging topics in this field. The novel clusters have shown unprecedented intramolecular electron-transfer features that can be directly mediated by the incorporated heteroanions. In this thesis, we will focus on the study of phosphite (HPO32-) as new non-traditional heteroanions, discover HPO32- templated nanostructures, investigate their electronic behaviours as well as understand the self-assembly process of HPO32--templated species. The thesis starts with incorporating HPO32- into POM cages. The feasibility of this work was illustrated by the successful trapping of HPO32- into a “Trojan Horse” type {W18O56} nanocage. The reactivity of embedded {HPO3} was fully studied, showing the cluster undergoes a structural rearrangement in solution whereby the {HPO3} moieties dimerise to form a weakly interacting (O3PH···HPO3) moiety. In the crystalline state a temperature-dependent intramolecular redox reaction and structural rearrangement occurs. This rearrangement appears to proceed via an intermediate containing two different templates, a pyramidal {HPO3} and a tetrahedral {PO4} moiety. {HPO3} templated POM cages were then vigorously expanded and led to the isolation of five either fully oxidised or mixed-valence clusters trapped with mono-, di-, or tri- {HPO3}. Interestingly, an intriguing 3D honeycomb-like host-guest structure was also synthesised. The porous framework was self-aggregated by a tri-phopshite anion templated {W21} cluster with a {VO4} templated Wells-Dawson type {W18} acting as a guest species within the hexagonal channels. Based on this work, we further extended the templating anions to two different redox-active heteroanions, and discovered a unique mixed-heteroatom templated system built by pairing redox-active {HPIIIO3} with {TeO3}, {SeO3} or {AsO3}. Two molecular systems were developed, ie. “Trojan Horse” type [W18O56(HPO3)0.8(SeO3)1.2(H2O)2]8- and cross-shaped [H4P4X4W64O224]32-/36-, where X=TeIV, SeIV, AsIII. In the case of {W18(HPO3)0.8(SeO3)1.2}, the compound is found to be a mixture of heteroleptic {W18(HPO3)(SeO3)} and homoleptic {W18(SeO3)2} and {W18(HPO3)2}, identified by single crystal x-ray diffraction, NMR as well as high resolution mass spectrometry. The cluster exhibited similar temperature-dependent electronic features to “Trojan Horse” type {W18(HPO3)2O56}. However, due to the intrinsic reactivity difference between {HPO3} and {SeO3}, the thermal treatment leads to the formation of an unusual species [W18O55(PO4)(SeO3)]5-, in which {HPO3} was fully oxidised to {PO4} within the cage, whereas and lone-pair-containing {SeO3} heteroanions were kept intact inside the shell. This finding is extremely interesting, as it demonstrated that multiple and independent intramolecular electronic performance can be achieved by the coexistence of distinct heteroatoms within a single molecule. On the other hand, the cross-shaped [H4P4X4W64O224]32-/36- were constructed by four {W15(HPO3)(XO3)} building units linked by four {WO6} octahedra. Each building unit traps two different heteroatoms. It is interesting to note that the mixed heteroatom species show self-sorting, with a highly selective positional preference. Smaller ionic sized {HPO3} are self-organised into the uncapped side of {W15} cavity, whereas closed side are occupied by larger heteroatoms, which is surprisingly opposed to steric hindrance. Density functional theory (DFT) calculations are currently underway to have a full understanding of the preference of heteroatom substitutions. This series of clusters is of great interest in terms of achieving single molecule-based heteroatom-dependent multiple levels of electron transfer. It has opened a new way to design and synthesise POMs with higher diversity of electrical states, which may lead to a new type of Q-bits for quantum computing. The third chapter is focused on developing polyoxotungstate building blocks templated by {HPO3}. A series of building blocks, {W15O48(HPO3)2}, {W9O30(HPO3)} {W12O40(HPO3)2} and hexagonal {W6O18(HPO3)} have been obtained. The first four building blocks have been reported with {SeO3} and/or {TeO3} heteroanions. This result demonstrates {HPO3} has a similar reactivity as {SeO3} and {TeO3}, therefore studying the self-assembly of {HPO3}-based building blocks would be helpful to have a general understanding of pyramidal heteroatom-based molecular systems. The hexagonal {W6O18(HPO3)} is observed for the first time in polyoxotungstates, showing some of reactivity difference between {HPO3} and {SeO3} and {TeO3}. Furthermore, inorganic salts and pH values have some directing influence on the formation and transformation of various building blocks, resulting in the discovery of a family of {HPO3}-based clusters with nuclearity ranging from {W29} to {W106}. High resolution mass spectrometry was also carried out to investigate the cluster solution behaviour and also gain information of building block speciation. It is found that some clusters experienced decomposition, which gives rise to potential building blocks accountable for the self-assembly.

Manipulating the structural and electronic properties of epitaxial NaNbO3 films via strain and stoichiometry

Due to their intriguing dielectric, pyroelectric, elasto-electric, or opto-electric properties, oxide ferroelectrics are vital candidates for the fabrication of most electronics. However, these extraordinary properties exist mainly in the temperature regime around the ferroelectric phase transition, which is usually several hundreds of K away from room temperature. Therefore, the manipulation of oxide ferroelectrics, especially moving the ferroelectric transition towards room temperature, is of great interest for application and also basic research. In this thesis, we demonstrate this using examples of NaNbO3 films. We show that the transition temperature of these films can be modified via plastic strain caused by epitaxial film growth on a structurally mismatched substrate, and this strain can be fixed by controlling the stoichiometry. The structural and electronic properties of Na1+xNbO3+δ thin films are carefully examined by among others XRD (e.g. RSM) and TEM and cryoelectronic measurements. Especially the electronic features are carefully analyzed via specially developed interdigitated electrodes in combination with integrated temperature sensor and heater. The electronic data are interpreted using existing as well as novel theories and models, they are proved to be closely correlated to the structural characteristics. The major results are: -Na1+xNbO3+δ thin films can be grown epitaxially on (110)NdGaO3 with a thickness up to 140 nm (thicker films have not been studied). Plastic relaxation of the compressive strain sets in when the thickness of the film exceeds approximately 10 – 15 nm. Films with excess Na are mainly composed of NaNbO3 with minor contribution of Na3NbO4. The latter phase seems to form nanoprecipitates that are homogeneously distributed in the NaNbO3 film which helps to stabilize the film and reduce the relaxation of the strain. -For the nominally stoichiometric films, the compressive strain leads to a broad and frequency-dispersive phase transition at lower temperature (125 – 147 K). This could be either a new transition or a shift in temperature of a known transition. Considering the broadness and frequency dispersion of the transition, this is actually a transition from the dielectric state at high temperature to a relaxor-type ferroelectric state at low temperature. The latter is based on the formation of polar nano-regions (PNRs). Using the electric field dependence of the freezing temperature, allows a direct estimation of the volume (70 to 270 nm3) and diameter (5.2 to 8 nm, spherical approximation) of the PNRs. The values confirm with literature values which were measured by other technologies. -In case of the off-stoichiometric samples, we observe again the classical ferroelectric behavior. However, the thermally hysteretic phase transition which is observed around 620 – 660 K for unstrained material is shifted to room temperature due to the compressive strain. Beside to the temperature shift, the temperature dependence of the permittivity is nearly identical for strained and unstrained materials. -The last but not least, in all cases, a significant anisotropy in the electronic and structural properties is observed which arises automatically from the anisotropic strain caused by the orthorhombic structure of the substrate. However, this anisotropy cannot be explained by the classical model which tries to fit an orthorhombic film onto an orthorhombic substrate. A novel “square lattice” model in which the films adapt a “square” shaped lattice in the plane of the film during the epitaxial growth at elevated temperature (~1000 K) nicely explains the experimental results. In this thesis we sketch a way to manipulate the ferroelectricity of NaNbO3 films via strain and stoichiometry. The results indicate that compressive strain which is generated by the epitaxial growth of the film on mismatched substrate is able to reduce the ferroelectric transition temperature or induce a phase transition at low temperature. Moreover, by adding Na in the NaNbO3 film a secondary phase Na3NbO4 is formed which seems to stabilize the main phase NaNbO3 and the strain and, thus, is able to engineer the ferroelectric behavior from the expected classical ferroelectric for perfect stoichiometry to relaxor-type ferroelectric for slightly off-stoichiometry, back to classical ferroelectric for larger off-stoichiometry. Both strain and stoichiometry are proven as perfect methods to optimize the ferroelectric properties of oxide films.

Utilizing Electronic Signatures and Electronic Form Filling to Streamline Document Approval Process

This CPM project focuses on the document approval process that the Division of State Human Resources consulting team utilizes as it relates to classification and compensation requests, e.g. job reclassifications, PD update requests, and salary requests. The ultimate goal is to become more efficient by utilizing electronic signatures and electronic form filling to streamline the current process of document approvals.

The public management issues of access to electronic gaming machines (EGMs) : a case study of policy in Victoria, its effects and requirements for evaluation

Wynne and Schaffer (2003) have highlighted both the strong growth of gambling activity in recent years, and the revenue streams this has generated for governments and communities. Gambling activities and the revenues derived from them have, unsurprisingly, therefore also been seen as a way in which to increase economic development in deprived areas (Jinkner-Lloyd, 1996). Consequently, according to Brown et al (2003), gambling is now a large taxation revenue earner for many western governments, at both federal and state levels, worldwide (for example UK, USA, Australia). In size and importance, the Australian gambling industry in particular has grown significantly over the last three decades, experiencing a fourfold increase in real gambling turnover. There are, however, also concerns expressed about gambling and Electronic Gaming in particular, as illustrated in economic, social and ethical terms in Oddo (1997). There are also spatial aspects to understanding these issues. Marshall’s (1998) study, for example, highlights that benefits from gambling are more likely to accrue at the macro as opposed to the local level, because of centralised tax gathering and spending of tax revenues, whilst localities may suffer from displacement of activities with higher multipliers than the institutions with EGMs that replace them. This also highlights a regional context of costs, where benefits accrue to the centre, but the costs accrue to the regions and localities, as simultaneously resources leave those communities through both the gambling activities themselves (in the form of revenue for the EGM owners), and the government (through taxes).

Dancing between diversity and consistency : refining assessment in postgraduate degrees in dance

This publication is the culmination of a 2 year Australian Learning and Teaching Council's Project Priority Programs Research Grant which investigates key issues and challenges in developing flexible guidelines lines for best practice in Australian Doctoral and Masters by Research Examination, encompassing the two modes of investigation, written and multi-modal (practice-led/based) theses, their distinctiveness and their potential interplay. The aims of the project were to address issues of assessment legitimacy raised by the entry of practice-orientated dance studies into Australian higher degrees; examine literal embodiment and presence, as opposed to cultural studies about states of embodiment; foreground the validity of questions around subjectivity and corporeal intelligence/s and the reliability of artistic/aesthetic communications, and finally to celebrate ‘performance mastery’(Melrose 2003) as a rigorous and legitimate mode of higher research. The project began with questions which centred around: the functions of higher degree dance research; concepts of 'master-ness’ and ‘doctorateness’; the kinds of languages, structures and processes which may guide candidates, supervisors, examiners and research personnel; the purpose of evaluation/examination; addressing positive and negative attributes of examination. Finally the study examined ways in which academic/professional, writing/dancing, tradition/creation and diversity/consistency relationships might be fostered to embrace change. Over two years, the authors undertook a qualitative national study encompassing a triangulation of semi-structured face to face interviews and industry forums to gather views from the profession, together with an analysis of existing guidelines, and recent literature in the field. The most significant primary data emerged from 74 qualitative interviews with supervisors, examiners, research deans and administrators, and candidates in dance and more broadly across the creative arts. Qualitative data gathered from the two primary sources, was coded and analysed using the NVivo software program. Further perspectives were drawn from international consultant and dance researcher Susan Melrose, as well as publications in the field, and initial feedback from a draft document circulated at the World Dance Alliance Global Summit in July 2008 in Brisbane. Refinement of data occurred in a continual sifting process until the final publication was produced. This process resulted in a set of guidelines in the form of a complex dynamic system for both product and process oriented outcomes of multi-modal theses, along with short position papers on issues which arose from the research such as contested definitions, embodiment and ephemerality, ‘liveness’ in performance research higher degrees, dissolving theory/practice binaries, the relationship between academe and industry, documenting practices and a re-consideration of the viva voce.

Dance dialogues : conversations across cultures, artforms and practices

These Proceedings, arising from the 2008 World Dance Alliance Global Summit, reflect both its spirit and diversity, re-appraising what dance is and might be in the 21st century. Through 53 papers from 14 countries in the Americas, Europe and the Asia-Pacific region, the authors — ranging from seasoned scholars to emerging artists publishing for the first time — span the perspectives of academics, educators, performance and community artists, health professionals and cognitive scientists; predominantly from dance but also from film, visual arts, science, performance and philosophy. The papers are grouped under the five Summit themes: Re-thinking the way we make Dance; Re-thinking the way we teach Dance; Mind/body connections; Transcultural conversations and Sustainability

Controlled growth of carbon nanotubes for electronic and photovoltaic applications

Carbon nanotubes (CNTs), experimentally observed for the first time twenty years ago, have triggered an unprecedented research effort, on the account of their astonishing structural, mechanical and electronic properties. Unfortunately, the current inability in predicting the CNTs’ properties and the difficulty in controlling their position on a substrate are often limiting factors for the application of this material in actual devices. This research aims at the creation of specific methodologies for controlled synthesis of CNTs, leading to effectively employ them in various fields of electronics, e.g. photovoltaics. Focused Ion Beam (FIB) patterning of Si surfaces is here proposed as a means for ordering the assembly of vertical-aligned CNTs. With this technique, substrates with specific nano-structured morphologies have been prepared, enabling a high degree of control over CNTs’ position and size. On these nano-structured substrates, the growth of CNTs has been realized by chemical vapor deposition (CVD), i.e. thermal decomposition of hydrocarbon gases over a heated catalyst. The most common materials used as catalysts in CVD are transition metals like Fe and Ni; however, their presence in the CNT products often results in shortcomings for electronic applications, especially for those based on silicon, being the metallic impurities incompatible with very-large-scale integration (VLSI) technology. In the present work the role of Ge dots as an alternative catalysts for CNTs synthesis on Si substrates has been thoroughly assessed, finding a close connection between the catalytic activity of such material and the CVD conditions, which can affect both size and morphology of the dots. Successful CNT growths from Ge dots have been obtained by CVD at temperatures ranging from 750 to 1000°C, with mixtures of acetylene and hydrogen in an argon carrier gas. The morphology of the Si surface is observed to play a crucial role for the outcome of the CNT synthesis: natural (i.e. chemical etching) and artificial (i.e. FIB patterning, nanoindentation) means of altering this morphology in a controlled way have been then explored to optimize the CNTs yield. All the knowledge acquired in this study has been finally applied to synthesize CNTs on transparent conductive electrodes (indium-tin oxide, ITO, coated glasses), for the creation of a new class of anodes for organic photovoltaics. An accurate procedure has been established which guarantees a controlled inclusion of CNTs on ITO films, preserving their optical and electrical properties. By using this set of conditions, a CNTenhanced electrode has been built, contributing to improve the power conversion efficiency of polymeric solar cells.

Homo- and heteronuclear meso,meso-(E)-Ethene-1,2-diyl-Linked Diporphyrins : preparation, X-ray crystal structure, electronic absorption and emission spectra and density functional theory calculations

Homo-and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M 210 (M 2=H 2/Ni, Ni 2, Ni/Zn, H 4, H 2Zn, Zn 2) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H 2, Ni, and ZnTriPP on the other (M 211), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, 1H NMR spectra, and for the Ni 2 bis(TriPP) complex Ni 210, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni II porphyrins, and the (E)-C 2H 2 bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H 410 and H 2Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni 210 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First-principle studies of electronic structure and C-doping effect in boron nitride nanoribbon

Structural and electronic properties have been studied for Boron Nitride nanoribbons (BNNR) with both zigzag and armchair shaped edge (Z-BNNR and A-BNNR) by first-principle spin-polarized total energy calculations. We found that the energy band gap of Z-BNNR is indirect and decreases monotonically with the increasing ribbon width, whereas direct energy band gap oscillation was observed for A-BNNRs. Additionally, C-substitution at either single boron or nitrogen atom site in BNNRs could induce spontaneous magnetization. Our results could be potentially useful to design magnetic nano-devices based on BNNRs.

The role of perceived usefulness and attitude on electronic health record acceptance : an empirical investigation using response surface analysis

Information and communications technologies are a significant component of the healthcare domain and electronic health records play a major role within it. As a result, it is important that they are accepted en masse by healthcare professionals. How healthcare professionals perceive the usefulness of electronic health records and their attitudes towards them have been shown to have significant effects on their overall acceptance. This paper investigates the role of perceived usefulness and attitude on the intention to use electronic health records by future healthcare professionals using polynomial regression with response surface analysis. Results show that the relationship is more complex than predicted in prior research. The paper concludes that the predicting properties of the above determinants must be further investigated to clearly understand their role in predicting the intention to use electronic health records and in designing systems that are better adopted by healthcare professionals of the future.

Mindfulness-meditation on the move : implementation of an ACT-based mindfulness practice intervention and training within a University Dance program

As part of the introduction of a broader dance medicine and science related health and wellbeing program, a 9 week mindfulness-meditation ACT-based program was delivered to all students undertaking full-time University dance training (N = 106). The aim of the program was to assist students in the further development of performance psychology skills that could be applied in both performance and non-performance settings. Participant groups were comprised of both male (N = 12) and female (N = 94) students from across all three year levels of two undergraduate dance courses, divided into three groups by mixed year levels due to timetable scheduling requirements. Pre- and post-testing was undertaken utilising the Mindful Attention Awareness Scale (MAAS-15), a uni-dimensional measure of mindfulness, in addition to qualitative questions checking the current level of awareness and understanding of mindfulness practice and its application. Weekly sessions were conducted by qualified sport and exercise psychologists and covered key practices such as: Mindfulness of Body, Mindfulness of Breathing, Mindfulness of Sounds, ACT-based and general Imagery exercises, Developing Open Awareness, Mindfulness of Emotions, and Developing Inner Stillness. Students were required to maintain a reflective journal that was utilised at the end of each weekly session, in addition to completion of a mid-Semester reflective debrief. Teaching staff additionally attended the weekly sessions and linked the mindfulness practice learnings into the student’s practical dance and academic classes where appropriate. Anecdotal feedback indicates that participation in the mindfulness-meditation sessions and the development of these mental skills has resulted in positive performance and personal outcomes. Observations collated from staff and students, results from the data collection phases and recommendations regarding future applications within dance training settings will be discussed within the presentation.

The role of perceived usefulness and attitude on electronic health record acceptance

Information and communications technologies are a significant component of the healthcare domain, and electronic health records play a major role in it. Therefore, it is important that they are accepted en masse by healthcare professionals. How healthcare professionals perceive the usefulness of electronic health records and their attitudes towards them have been shown to have significant effects on the overall acceptance in many healthcare systems around the world. This paper investigates the role of perceived usefulness and attitude on the intention to use electronic health records by future healthcare professionals using polynomial regression with response surface analysis. Results show that the relationships between these variables are more complex than predicted in prior research. The paper concludes that the properties of the above determinants must be further investigated to clearly understand: (i) their role in predicting the intention to use electronic health records; and (ii) in designing systems that are better adopted by healthcare professionals of the future.

Structural, electronic, and optical properties of wurtzite and rocksalt InN under pressure

Structural stability, electronic, and optical properties of InN under high pressure are studied using the first-principles calculations. The lattice constants and electronic band structure are found consistent with the available experimental and theoretical values. The pressure of the wurtzite-to-rocksalt structural transition is 13.4 GPa, which is in an excellent agreement with the most recent experimental values. The optical characteristics reproduce the experimental data thus justifying the feasibility of our theoretical predictions of the optical properties of InN at high pressures.

Cresols - An investigation into their electronic structure and spectra

The three isomeric cresols were subjected to the all-valence-electron CNDO/2 andPPP-CI calculations. Results from this study were used: (i) to compare the electronic structures of these isomers vis-Ã-vis parent compounds-phenol and toluene, (ii) to obtain a quantitative picture of their chemical reactivities and electronic absorption spectra. Using the sgr-core charges derived from CNDO/2 calculations and subsequently revising the valence-state ionisation potential and one-center-two-electron repulsion integrals, thePPP-CI calculations were performed on the title compounds according toNishimoto andForster scheme. In these calculations the pseudo-unsaturated nature of the methyl group has been given due consideration. In spectral assignment, compared to the conventionalPPP approach, the CNDO/2-basedPPP-CI method gave a better agreement with the experimental data.

Electronic structure and bonding of beta-rhombohedral boron using cluster fragment approach

Theoretical studies using density functional theory are carried out to understand the electronic structure and bonding and electronic properties of elemental beta-rhombohedral boron. The calculated band structure of ideal beta-rhombohedral boron (B-105) shows valence electron deficiency and depicts metallic behavior. This is in contrast to the experimental result that it is a semiconductor. To understand this ambiguity we discuss the electronic structure and bonding of this allotrope with cluster fragment approach using our recently proposed mno rule. This helps us to comprehend in greater detail the structure of B-105 and materials which are closely related to beta-rhombohedral boron. The molecular structures B12H12-2, B28H21+1, BeB27H21, LiB27H21-1, CB27H21+2, B57H36+3, Be3B54H36, and Li2CB54H36, and corresponding solids Li8Be3B102 and Li10CB102 are arrived at using these ideas and studied using first principles density functional theory calculations.