Sex offenders in denial : a study into a group of forensic psychologists' attitudes regarding the corresponding impact upon risk assessment calculations and parole eligibility

A considerable proportion of convicted sex offenders maintain a stance of innocence and thus do not engage in recommended treatment programs. As a result, such offenders are often deemed to have outstanding criminogenic needs which may negatively impact upon risk assessment procedures and parole eligibility. This paper reports on a study that aimed to investigate a group of forensic psychologists’ attitudes regarding the impact of denial on risk assessment ratings as well as parole eligibility. Participants completed a confidential open-ended questionnaire. Analysis indicated that considerable variability exists among forensic psychologists in regards to their beliefs about the origins of denial and what impact such denial should have on post-prison release eligibility. In contrast, there was less disparity regarding beliefs about the percentage of innocent yet incarcerated sex offenders. This paper also reviews current understanding regarding the impact of denial on recidivism as well as upon general forensic assessments.

Emergency department surge capacity : Recommendations of the Australasian surge strategy working group

Background For more than a decade emergency medicine organizations have produced guidelines, training and leadership for disaster management. However to date, there have been limited guidelines for emergency physicians needing to provide a rapid response to a surge in demand. The aim of this study is to identify strategies which may guide surge management in the Emergency Department. Method A working group of individuals experienced in disaster medicine from the Australasian College for Emergency Medicine Disaster Medicine Subcommittee (the Australasian Surge Strategy Working Group) was established to undertake this work. The Working Group used a modified Delphi technique to examine response actions in surge situations. The Working Group identified underlying assumptions from epidemiological and empirical understanding and then identified remedial strategies from literature and from personal experience and collated these within domains of space, staff, supplies, and system operation. Findings These recommendations detail 22 potential actions available to an emergency physician working in the context of surge. The Working Group also provides detailed guidance on surge recognition, triage, patient flow through the emergency department and clinical goals and practices. Discussion These strategies provide guidance to emergency physicians confronting the challenges of a surge in demand. The paper also identifies areas that merit future research including the measurement of surge capacity, constraints to strategy implementation, validation of surge strategies and measurement of strategy impacts on throughput, cost, and quality of care.

A phenomenological study of contemplative experiences : implications for interior design

This research reports on a project concerned with the relationship between the person and the environment in the context of achieving a contemplative or existential state – a state which can be experienced either consciously or subconsciously. The need for such a study originated with the desire to contribute to the design of multicultural spaces which could be used for a range of activities within the public and the personal arena, activities including contemplation, meditation and prayer. The concept of ‘sacred’ is explored in the literature review and in primary interviews with the participants of this study. Given that the word ‘sacred’ is highly value-laden and potentially alienating for some people, it was decided to use the more accessible term ‘contemplative’. The outcomes of the study inform the practice of interior design and architecture which tends currently to neglect the potential for all spaces to be existentially meaningful. Informed by phenomenological methodology, data were collected from a diverse group of people, using photo-elicitation and interviews. The technique of photo-elicitation proved to be highly effective in helping people reveal their everyday lived experience of contemplative spaces. Reflective analysis (Van Manen 2000) was used to explore the data collected. The initial stage of analysis produced three categories of data: varying conceptions of contemplation, aspects of the person involved in the contemplation, and aspects of environment involved in contemplation. From this, it was found that achieving a state of contemplation involves both the person and the environment in a dialectic process of unfolding. The unfolding has various physical, psycho-social, and existential dimensions or qualities which operate sequentially and simultaneously. Two concepts emerged as being central to unfolding: ‘Cleansing’ and ‘Nothingness’. Unfolding is found to comprise the Core; Distinction; Manifestation; Cleansing; Creation; and Sharing. This has a parallel with Mircea Eliade’s (1959) definition of sacred as something that manifests itself as different from the profane. The power of design, re-contextualization through utility and purpose, and the existential engagements between the person and environment are used as a basis for establishing the potential contribution of the study to interior design. In this way, the study makes a contribution to our understanding of how space and its elements inspire, support and sustain person environment interaction – particularly at the existential level – as well as to our understanding of the multi-dimensional and holistic nature of this interaction. In addition, it points to the need for a phenomenological re-conceptualisation of the design/client relationship. In summary, the contributions of this research are: the exploration of contemplative experience as sacred experience; an understanding of the design of space as creating engagement between person and environment; a rationale for the introduction of a phenomenological approach to the relationship between designer and clients; and raising awareness of the spiritual in a holistic approach to design.

Theoretical investigation of thermal tweezers for parallel manipulation of atoms and nanoparticles on surfaces

A major focus of research in nanotechnology is the development of novel, high throughput techniques for fabrication of arbitrarily shaped surface nanostructures of sub 100 nm to atomic scale. A related pursuit is the development of simple and efficient means for parallel manipulation and redistribution of adsorbed atoms, molecules and nanoparticles on surfaces – adparticle manipulation. These techniques will be used for the manufacture of nanoscale surface supported functional devices in nanotechnologies such as quantum computing, molecular electronics and lab-on-achip, as well as for modifying surfaces to obtain novel optical, electronic, chemical, or mechanical properties. A favourable approach to formation of surface nanostructures is self-assembly. In self-assembly, nanostructures are grown by aggregation of individual adparticles that diffuse by thermally activated processes on the surface. The passive nature of this process means it is generally not suited to formation of arbitrarily shaped structures. The self-assembly of nanostructures at arbitrary positions has been demonstrated, though these have typically required a pre-patterning treatment of the surface using sophisticated techniques such as electron beam lithography. On the other hand, a parallel adparticle manipulation technique would be suited for directing the selfassembly process to occur at arbitrary positions, without the need for pre-patterning the surface. There is at present a lack of techniques for parallel manipulation and redistribution of adparticles to arbitrary positions on the surface. This is an issue that needs to be addressed since these techniques can play an important role in nanotechnology. In this thesis, we propose such a technique – thermal tweezers. In thermal tweezers, adparticles are redistributed by localised heating of the surface. This locally enhances surface diffusion of adparticles so that they rapidly diffuse away from the heated regions. Using this technique, the redistribution of adparticles to form a desired pattern is achieved by heating the surface at specific regions. In this project, we have focussed on the holographic implementation of this approach, where the surface is heated by holographic patterns of interfering pulsed laser beams. This implementation is suitable for the formation of arbitrarily shaped structures; the only condition is that the shape can be produced by holographic means. In the simplest case, the laser pulses are linearly polarised and intersect to form an interference pattern that is a modulation of intensity along a single direction. Strong optical absorption at the intensity maxima of the interference pattern results in approximately a sinusoidal variation of the surface temperature along one direction. The main aim of this research project is to investigate the feasibility of the holographic implementation of thermal tweezers as an adparticle manipulation technique. Firstly, we investigate theoretically the surface diffusion of adparticles in the presence of sinusoidal modulation of the surface temperature. Very strong redistribution of adparticles is predicted when there is strong interaction between the adparticle and the surface, and the amplitude of the temperature modulation is ~100 K. We have proposed a thin metallic film deposited on a glass substrate heated by interfering laser beams (optical wavelengths) as a means of generating very large amplitude of surface temperature modulation. Indeed, we predict theoretically by numerical solution of the thermal conduction equation that amplitude of the temperature modulation on the metallic film can be much greater than 100 K when heated by nanosecond pulses with an energy ~1 mJ. The formation of surface nanostructures of less than 100 nm in width is predicted at optical wavelengths in this implementation of thermal tweezers. Furthermore, we propose a simple extension to this technique where spatial phase shift of the temperature modulation effectively doubles or triples the resolution. At the same time, increased resolution is predicted by reducing the wavelength of the laser pulses. In addition, we present two distinctly different, computationally efficient numerical approaches for theoretical investigation of surface diffusion of interacting adparticles – the Monte Carlo Interaction Method (MCIM) and the random potential well method (RPWM). Using each of these approaches we have investigated thermal tweezers for redistribution of both strongly and weakly interacting adparticles. We have predicted that strong interactions between adparticles can increase the effectiveness of thermal tweezers, by demonstrating practically complete adparticle redistribution into the low temperature regions of the surface. This is promising from the point of view of thermal tweezers applied to directed self-assembly of nanostructures. Finally, we present a new and more efficient numerical approach to theoretical investigation of thermal tweezers of non-interacting adparticles. In this approach, the local diffusion coefficient is determined from solution of the Fokker-Planck equation. The diffusion equation is then solved numerically using the finite volume method (FVM) to directly obtain the probability density of adparticle position. We compare predictions of this approach to those of the Ermak algorithm solution of the Langevin equation, and relatively good agreement is shown at intermediate and high friction. In the low friction regime, we predict and investigate the phenomenon of ‘optimal’ friction and describe its occurrence due to very long jumps of adparticles as they diffuse from the hot regions of the surface. Future research directions, both theoretical and experimental are also discussed.

Three-dimensional hydrogen-bonded structures in the 1:1 proton-transfer compounds of L-tartaric acid with the associative-group monosubstituted pyridines 3-minopyridine, 3-carboxypyridine (nicotinic acid) and 2-carboxypyridine (picolinic acid).

The 1:1 proton-transfer compounds of L-tartaric acid with 3-aminopyridine [3-aminopyridinium hydrogen (2R,3R)-tartrate dihydrate, C5H7N2+·C4H5O6-·2H2O, (I)], pyridine-3-carboxylic acid (nicotinic acid) [anhydrous 3-carboxypyridinium hydrogen (2R,3R)-tartrate, C6H6NO2+·C4H5O6-, (II)] and pyridine-2-carboxylic acid [2-carboxypyridinium hydrogen (2R,3R)-tartrate monohydrate, C6H6NO2+·C4H5O6-·H2O, (III)] have been determined. In (I) and (II), there is a direct pyridinium-carboxyl N+-HO hydrogen-bonding interaction, four-centred in (II), giving conjoint cyclic R12(5) associations. In contrast, the N-HO association in (III) is with a water O-atom acceptor, which provides links to separate tartrate anions through Ohydroxy acceptors. All three compounds have the head-to-tail C(7) hydrogen-bonded chain substructures commonly associated with 1:1 proton-transfer hydrogen tartrate salts. These chains are extended into two-dimensional sheets which, in hydrates (I) and (III) additionally involve the solvent water molecules. Three-dimensional hydrogen-bonded structures are generated via crosslinking through the associative functional groups of the substituted pyridinium cations. In the sheet struture of (I), both water molecules act as donors and acceptors in interactions with separate carboxyl and hydroxy O-atom acceptors of the primary tartrate chains, closing conjoint cyclic R44(8), R34(11) and R33(12) associations. Also, in (II) and (III) there are strong cation carboxyl-carboxyl O-HO hydrogen bonds [OO = 2.5387 (17) Å in (II) and 2.441 (3) Å in (III)], which in (II) form part of a cyclic R22(6) inter-sheet association. This series of heteroaromatic Lewis base-hydrogen L-tartrate salts provides further examples of molecular assembly facilitated by the presence of the classical two-dimensional hydrogen-bonded hydrogen tartrate or hydrogen tartrate-water sheet substructures which are expanded into three-dimensional frameworks via peripheral cation bifunctional substituent-group crosslinking interactions.

The creative sector in New Zealand : mapping and economic role : report to New Zealand Trade and Enterprise

The New Zealand creative sector was responsible for almost 121,000 jobs at the time of the 2006 Census (6.3% of total employment). These are divided between • 35,751 creative specialists – persons employed doing creative work in creative industries • 42,300 support workers - persons providing management and support services in creative industries • 42,792 embedded creative workers – persons engaged in creative work in other types of enterprise The most striking feature of this breakdown is the fact that the largest group of creative workers are employed outside the creative industries, i.e. in other types of businesses. Even within the creative industries, there are fewer people directly engaged in creative work than in providing management and support. Creative sector employees earned incomes of approximately $52,000 per annum at the time of the 2006 Census. This is relatively uniform across all three types of creative worker, and is significantly above the average for all employed persons (of approximately $40,700). Creative employment and incomes were growing strongly over both five year periods between the 1996, 2001 and 2006 Censuses. However, when we compare creative and general trends, we see two distinct phases in the development of the creative sector: • rapid structural growth over the five years to 2001 (especially led by developments in ICT), with creative employment and incomes increasing rapidly at a time when they were growing modestly across the whole economy; • subsequent consolidation, with growth driven by more by national economic expansion than structural change, and creative employment and incomes moving in parallel with strong economy-wide growth. Other important trends revealed by the data are that • the strongest growth during the decade was in embedded creative workers, especially over the first five years. The weakest growth was in creative specialists, with support workers in creative industries in the middle rank, • by far the strongest growth in creative industries’ employment was in Software & digital content, which trebled in size over the decade Comparing New Zealand with the United Kingdom and Australia, the two southern hemisphere nations have significantly lower proportions of total employment in the creative sector (both in creative industries and embedded employment). New Zealand’s and Australia’s creative shares in 2001 were similar (5.4% each), but in the following five years, our share has expanded (to 5.7%) whereas Australia’s fell slightly (to 5.2%) – in both cases, through changes in creative industries’ employment. The creative industries generated $10.5 billion in total gross output in the March 2006 year. Resulting from this was value added totalling $5.1b, representing 3.3% of New Zealand’s total GDP. Overall, value added in the creative industries represents 49% of industry gross output, which is higher than the average across the whole economy, 45%. This is a reflection of the relatively high labour intensity and high earnings of the creative industries. Industries which have an above-average ratio of value added to gross output are usually labour-intensive, especially when wages and salaries are above average. This is true for Software & Digital Content and Architecture, Design & Visual Arts, with ratios of 60.4% and 55.2% respectively. However there is significant variation in this ratio between different parts of the creative industries, with some parts (e.g. Software & Digital Content and Architecture, Design & Visual Arts) generating even higher value added relative to output, and others (e.g. TV & Radio, Publishing and Music & Performing Arts) less, because of high capital intensity and import content. When we take into account the impact of the creative industries’ demand for goods and services from its suppliers and consumption spending from incomes earned, we estimate that there is an addition to economic activity of: • $30.9 billion in gross output, $41.4b in total • $15.1b in value added, $20.3b in total • 158,100 people employed, 234,600 in total The total economic impact of the creative industries is approximately four times their direct output and value added, and three times their direct employment. Their effect on output and value added is roughly in line with the average over all industries, although the effect on employment is significantly lower. This is because of the relatively high labour intensity (and high earnings) of the creative industries, which generate below-average demand from suppliers, but normal levels of demand though expenditure from incomes. Drawing on these numbers and conclusions, we suggest some (slightly speculative) directions for future research. The goal is to better understand the contribution the creative sector makes to productivity growth; in particular, the distinctive contributions from creative firms and embedded creative workers. The ideas for future research can be organised into the several categories: • Understanding the categories of the creative sector– who is doing the business? In other words, examine via more fine grained research (at a firm level perhaps) just what is the creative contribution from the different aspects of the creative sector industries. It may be possible to categorise these in terms of more or less striking innovations. • Investigate the relationship between the characteristics and the performance of the various creative industries/ sectors; • Look more closely at innovation at an industry level e.g. using an index of relative growth of exports, and see if this can be related to intensity of use of creative inputs; • Undertake case studies of the creative sector; • Undertake case studies of the embedded contribution to growth in the firms and industries that employ them, by examining taking several high performing noncreative industries (in the same way as proposed for the creative sector). • Look at the aggregates – drawing on the broad picture of the extent of the numbers of creative workers embedded within the different industries, consider the extent to which these might explain aspects of the industries’ varied performance in terms of exports, growth and so on. • This might be able to extended to examine issues like the type of creative workers that are most effective when embedded, or test the hypothesis that each industry has its own particular requirements for embedded creative workers that overwhelms any generic contributions from say design, or IT.

Mechanisms of change in negative thinking and urinary monoamines in depressed patients during acute treatment with group cognitive behavior therapy and antidepressant medication

This naturalistic study investigated the mechanisms of change in measures of negative thinking and in 24-h urinary metabolites of noradrenaline (norepinephrine), dopamine and serotonin in a sample of 43 depressed hospital patients attending an eight-session group cognitive behavior therapy program. Most participants (91%) were taking antidepressant medication throughout the therapy period according to their treating Psychiatrists' prescriptions. The sample was divided into outcome categories (19 Responders and 24 Non-responders) on the basis of a clinically reliable change index [Jacobson, N.S., & Truax, P., 1991. Clinical significance: a statistical approach to defining meaningful change in psychotherapy research. Journal of Consulting and Clinical Psychology, 59, 12–19.] applied to the Beck Depression Inventory scores at the end of the therapy. Results of repeated measures analysis of variance [ANOVA] analyses of variance indicated that all measures of negative thinking improved significantly during therapy, and significantly more so in the Responders as expected. The treatment had a significant impact on urinary adrenaline and metadrenaline excretion however, these changes occurred in both Responders and Non-responders. Acute treatment did not significantly influence the six other monoamine metabolites. In summary, changes in urinary monoamine levels during combined treatment for depression were not associated with self-reported changes in mood symptoms.

Skydweller and representations of the adolescent crisis : group identity versus alienation

This document contains a creative work – the text of a young adult novel, Skydweller – and an exegesis discussing the ways in which identity and the adolescent crisis of group identity versus alienation are represented in young adult science fiction/fantasy novels.

Hydrate stabilization in the three-dimensional hydrogen-bonded structure of the brucinium compound, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4'-disulfonate hexahydrate

The crystal structure of the 2:1 proton-transfer compound of brucine with biphenyl-4,4’-disulfonate, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4'-disulfonate hexahydrate (1) has been determined at 173 K. Crystals are monoclinic, space group P21 with Z = 2 in a cell with a = 8.0314(2), b = 29.3062(9), c = 12.2625(3) Å, β = 101.331(2)o. The crystallographic asymmetric unit comprises two brucinium cations, a biphenyl-4,4'-disulfonate dianion and six water molecules of solvation. The brucinium cations form a variant of the common undulating and overlapping head-to-tail sheet sub-structure. The sulfonate dianions are also linked head-to-tail by hydrogen bonds into parallel zig-zag chains through clusters of six water molecules of which five are inter-associated, featuring conjoint cyclic eight-membered hydrogen-bonded rings [graph sets R33(8) and R34(8)], comprising four of the water molecules and closed by sulfonate O-acceptors. These chain structures occupy the cavities between the brucinium cation sheets and are linked to them peripherally through both brucine N+-H...Osulfonate and Ocarbonyl…H-Owater to sulfonate O bridging hydrogen bonds, forming an overall three-dimensional framework structure. This structure determination confirms the importance of water in the stabilization of certain brucine compounds which have inherent crystal instability.

Homophobia, heteronormativism and hegemonic masculinity : male same-sex intimate violence from the perspective of Brisbane service providers

Few studies have explored the problem of male same-sex intimate partner violence, especially in the context of Australia. Utilizing in-depth interviews with gay-friendly service providers in Brisbane, the research presented in this article sought to ascertain whether (a) intimate partner violence occurs in male same-sex intimate relationships, (b)if so, what form this violence takes,(c) what contextual triggers underpin this violence,(d) what barriers victims face in exiting abusive relationships and seeking support, and (e) what services are available and appropriate to the needs of men in violent intimate relationships with other men. Results suggest that the prevalence, types and contextual triggers of violence in male same-sex relationships parallel abuse in opposite-sex relationships. Heteronormativism, homophobia, and its close association with hegemonic masculinity, however, emerge as features unique to the male same-sex intimate partner violence experience.

Red clover (Trifolium pratense) isoflavones and serum homocysteine in premenopausal women : a pilot study

Background: There is limited information on the effect of isoflavones on homocysteine concentrations, a risk factor for a number of chronic diseases. Methods: Twenty-three premenopausal women participated in a double-blind, randomized, parallel study for four menstrual cycles. Subjects consumed either placebo or purified red clover (Trifolium pratense) isoflavone (86mg/day) tablets. Blood samples were collected weekly during cycles 1, 3, and 4 for determination of serum folate and total homocysteine concentrations. Dietary intake was monitored monthly. Results: Concentrations of folate and homocysteine in serum did not change significantly in either group, and there were no significant differences observed between the follicular and luteal phases of the menstrual cycle. The participants' dietary records indicated that nutrient intake was constant, and compliance was confirmed by analysis of urinary isoflavone concentrations and tablet counts in returned containers. Conclusions: These results suggest that in the absence of any dietary modification, supplementation with purified isoflavones that are predominantly methoxylated has no effect on serum homocysteine or folate in premenopausal women.

A peptidomimetic inhibitor of matrix metalloproteinases containing a tetherable linker group

Successful wound repair and normal turnover of the extracellular matrix relies on a balance between matrix metalloproteinases (MMPs) and their natural inhibitors (the TIMPs). When over-expression of MMPs and abnormally high levels of activation or low expression of TIMPs are encountered, excessive degradation of connective tissue and the formation of chronic ulcers can occur. One strategy to rebalance MMPs and TIMPs is to use inhibitors. We have designed a synthetic pseudopeptide inhibitor with an amine linker group based on a known high-affinity peptidomimetic MMP inhibitor have demonstrated inhibition of MMP-1, -2, -3 and -9 activity in standard solutions. The inhibitor was also tethered to a polyethylene glycol hydrogel using a facile reaction between the linker unit on the inhibitor and the hydrogel precursors. After tethering, we observed inhibition of the MMPs although there was an increase in the IC50s which was attributed to poor diffusion of the MMPs into the hydrogels, reduced activity of the tethered inhibitor or incomplete incorporation of the inhibitor into the hydrogels. When the tethered inhibitors were tested against chronic wound fluid we observed significant inhibition in proteolytic activity suggesting our approach may prove useful in rebalancing MMPs within chronic wounds.

Elliptic curves, group law, and efficient computation

This thesis is about the derivation of the addition law on an arbitrary elliptic curve and efficiently adding points on this elliptic curve using the derived addition law. The outcomes of this research guarantee practical speedups in higher level operations which depend on point additions. In particular, the contributions immediately find applications in cryptology. Mastered by the 19th century mathematicians, the study of the theory of elliptic curves has been active for decades. Elliptic curves over finite fields made their way into public key cryptography in late 1980’s with independent proposals by Miller [Mil86] and Koblitz [Kob87]. Elliptic Curve Cryptography (ECC), following Miller’s and Koblitz’s proposals, employs the group of rational points on an elliptic curve in building discrete logarithm based public key cryptosystems. Starting from late 1990’s, the emergence of the ECC market has boosted the research in computational aspects of elliptic curves. This thesis falls into this same area of research where the main aim is to speed up the additions of rational points on an arbitrary elliptic curve (over a field of large characteristic). The outcomes of this work can be used to speed up applications which are based on elliptic curves, including cryptographic applications in ECC. The aforementioned goals of this thesis are achieved in five main steps. As the first step, this thesis brings together several algebraic tools in order to derive the unique group law of an elliptic curve. This step also includes an investigation of recent computer algebra packages relating to their capabilities. Although the group law is unique, its evaluation can be performed using abundant (in fact infinitely many) formulae. As the second step, this thesis progresses the finding of the best formulae for efficient addition of points. In the third step, the group law is stated explicitly by handling all possible summands. The fourth step presents the algorithms to be used for efficient point additions. In the fifth and final step, optimized software implementations of the proposed algorithms are presented in order to show that theoretical speedups of step four can be practically obtained. In each of the five steps, this thesis focuses on five forms of elliptic curves over finite fields of large characteristic. A list of these forms and their defining equations are given as follows: (a) Short Weierstrass form, y2 = x3 + ax + b, (b) Extended Jacobi quartic form, y2 = dx4 + 2ax2 + 1, (c) Twisted Hessian form, ax3 + y3 + 1 = dxy, (d) Twisted Edwards form, ax2 + y2 = 1 + dx2y2, (e) Twisted Jacobi intersection form, bs2 + c2 = 1, as2 + d2 = 1, These forms are the most promising candidates for efficient computations and thus considered in this work. Nevertheless, the methods employed in this thesis are capable of handling arbitrary elliptic curves. From a high level point of view, the following outcomes are achieved in this thesis. - Related literature results are brought together and further revisited. For most of the cases several missed formulae, algorithms, and efficient point representations are discovered. - Analogies are made among all studied forms. For instance, it is shown that two sets of affine addition formulae are sufficient to cover all possible affine inputs as long as the output is also an affine point in any of these forms. In the literature, many special cases, especially interactions with points at infinity were omitted from discussion. This thesis handles all of the possibilities. - Several new point doubling/addition formulae and algorithms are introduced, which are more efficient than the existing alternatives in the literature. Most notably, the speed of extended Jacobi quartic, twisted Edwards, and Jacobi intersection forms are improved. New unified addition formulae are proposed for short Weierstrass form. New coordinate systems are studied for the first time. - An optimized implementation is developed using a combination of generic x86-64 assembly instructions and the plain C language. The practical advantages of the proposed algorithms are supported by computer experiments. - All formulae, presented in the body of this thesis, are checked for correctness using computer algebra scripts together with details on register allocations.

Spectroscopy of selected copper group minerals : chalcophyllite and chenevixite-implications for hydrogen bonding

NIR and IR spectroscopy has been applied for detection of chemical species and the nature of hydrogen bonding in arsenate complexes. The structure and spectral properties of copper(II) arsenate minerals chalcophyllite and chenevixite are compared with copper(II) sulphate minerals devilline, chalcoalumite and caledonite. Split NIR bands in the electronic spectrum of two ranges 11700-8500 cm-1 and 8500-7200 cm-1 confirm distortion of octahedral symmetry for Cu(II) in the arsenate complexes. The observed bands with maxima at 9860 and 7750 cm-1 are assigned to Cu(II) transitions 2B1g ® 2B2g and 2B1g ® 2A1g. Overlapping bands in the NIR region 4500-4000 cm-1 is the effect of multi anions OH-, (AsO4)3- and (SO4)2-. The observation of broad and diffuse bands in the range 3700-2900 cm-1 confirms strong hydrogen bonding in chalcophyllite relative to chenevixite. The position of the water bending vibrations indicates the water is strongly hydrogen bonded in the mineral structure. The strong absorption feature centred at 1644 cm-1 in chalcophyllite indicates water is strongly hydrogen bonded in the mineral structure. The H2O-bending vibrations shift to low wavenumbers in chenevixite and an additional band observed at 1390 cm-1 is related to carbonate impurity. The characterisation of IR spectra by ν3 antisymmetric stretching vibrations of (SO4)2- and (AsO4)3 ions near 1100 and 800 cm-1 respectively is the result of isomorphic substitution for arsenate by sulphate in both the minerals of chalcophyllite and chenevixite.