VictorJuiz/thesis huggingface dataset:
Photoelectron spectroscopy in inorganic chemistry

The ultra-violet and X-ray photoelectron spectra of the tris-hexafluoroacetylacetonato complexes of cone transition metals are reported and discussed. For many of these complexes there is either little or no literature experimental data available and, where necessary full details have been given in this thesis, both of the preparation and purification of the complexes. The gas-phase ultra-violet photoelectron spectra are discussed first, and it is shown how the spectra lead unambiguously to an energy level ordering similar to that assumed in ligand-field theory. However, in the high-spin complexes of Mn(III) and Fe(III) and in the low-spin Co(III) complex, the metal levels are observed to have ionisation energies which, for the most part, are higher than those of the least stable ligand molecular orbitals. This is in direct contradiction to the predictions of ligand-field theory and, in the case of the Co(III) complex, leads to an inversion of the trigonally split e and a1, metal d orbitals. The interpretation of the high-spin complex spectra is shown to be very difficult within the one-electron framework used for the other complexes and the ultra-violet spectra are shown to be the best guide to interpretation. The values for the ligand-field parameters so derived are similar to, though slightly larger than, those for the neutral species.
The ESCA spectra of the complexes were measured and are reported in the second part of the thesis. The movements of the core levels so found are related by an expression derived by Siegbahn et al. to the charge shifts in the complexes as the metal is changed. These charge shifts are of three basic types: a polarisation of the andpi; framework of the ligand towards the metal as the metal-oxygen bond length contracts, a transfer of charge from the ligand andsigma;-system to the metal, increasing as the transition series is traversed and a charge shift from the anti-bonding metal d-orbitals back onto the andsigma;-system of the ligand as a natural consequence of its anti-bonding character.
As a parallel study, the ESCA spectra of the metallocenes were also run and are reported at the end of the second part of the thesis. The charge shifts observed in these compounds show a remarkable parallel to those found in the hexafluoroacetylacetonato complexes, when the different metal charges and ligand characteristics are taken into account. These trends were shown to be in accord with other data on the metallocenes.
In the last part of the thesis, the charge and orbital energy shifts deduced in the first two parts of the thesis for the hexafluoroacetylacetonato complexes are correlated with other physical measurements and a consistent picture of the bonding in these complexes shown to emerge. In particular, the shifts in ionisation energies found for many of the main bands in the ultra-violet photoelectron spectra receive a ready explanation once the ESCA data is considered. On this basis a case is made for the complementarity of the two techniques.

Advisor: Orchard, A
Towards a theory of adjudication: some issues of method and principle

A sound theory of adjudication and of judicial duty requires or presupposes a sound theory of law and of legal argument. Jurisprudential inquiry is properly grounded not in reflections on conceptual properties of law but in reflections on human goods and needs as understood in a morally articulated theory of practical reason and compactly expressed in the normative concept of the common good. Such reflections confirm that law exists, in its central case, as a means to various types of authoritative co-ordination solutions. The underdetermined nature of (a) the positive requirements of practical reasonableness and the common good and of (b) the appropriate means of enforcing compliance and remedying non-compliance with either these requirements or the determinate negative precepts of practical reasonableness entails that a practically necessary aspect of the positive law’s role is constituting the requirements of justice, i.e. of what is due to whom generally and in particular situations (including situations where an injustice has been or is alleged to have been done). As a distinct and practically necessary mode of legal co-ordination for the common good, adjudication, in its central case, answers litigated questions of justice by applying all relevant law in accordance with the legal system’s practice of legal argument. Thus adjudication is performed by authoritative law-applying institutions precisely because it is about answering questions of justice, and not despite that fact. Theories of law developed on the assumption that it is possible to understand the ‘what’ of law without reliance on any moral judgments deny any practically necessary connection between (a) the promotion of justice and the common good and (b) the nature of law, in its central case, and, hence, the adjudicative application of the law. In the absence of this connection a judicial duty to do justice according to law is unintelligible.

Keywords: Natural Law
Adjudication
Judicial Duty
Jurisprudence
Methodology
Thomas Aquinas
John Finnis
Advisor: Finnis, J
Confronting the juggernaut of extraction: local, national and transnational mobilisation against the Phulbari coal mine in Bangladesh

A massive open-cast coal mine was proposed for Phulbari in 1994, with the support of the government and international financial organisations. Threatened by displacement, the apparently powerless community mobilised against the mine. Allied with the national and the transnational activist organisations, they successfully stopped the mine. This remarkable success is the subject of the thesis.
This resistance is compared quantitatively with the incidence of protests in 397 other mines in the South Asia. Predictors of protest include density of population, proportion of area under forest cover, and ownership by a multinational company. These factors alone would predict a high probability of protest in Phulbari. To understand how the resistance unfolded and why it was successful, the thesis relies on ethnographic evidence. I conducted participant observation and interviewed sixty-four individuals in Phulbari and Dhaka in Bangladesh and in London.
Mobilisation against the mine can be explained in part by dialogic framing. Local challengers continuously opposed the dominant discourse of development. Crucially, they shifted their identity to legitimize their opposition to the mine by tagging it with nationalism. As a result, local resistance established links with national left-wing activists. Mobilisation culminated in a mass march of 70,000 in 2006, which was fired on by government forces, with several casualties. Repression failed to quail the resistance. Continued mobilisation was motivated by emotional responses like anger, and facilitated by cultural practices like the obligatory funeral procession.
Media reports of the repression catapulted the resistance on to the global stage. This alone is not sufficient to explain the formation of a transnational alliance against the mine. This was maintained by the presence of a large community of Bangladeshi living in Britain, and the mediating role of the left-wing activists in Bangladesh; both groups could translate between locals and western NGOs. This transnational coalition impeded the mining company by targeting international financial organisations, Western governments, the government of Bangladesh, and investors in London. As a result, the company’s share price has collapsed and there seems little prospect of the project proceeding.

Keywords: mining
protests
displacement
environment
national interest
Advisor: Biggs, M
Signal compatibility as a modulatory factor for audiovisual multisensory integration

The physical properties of the distal stimuli activating our senses are often correlated in nature; it would therefore be advantageous to exploit such correlations to better process sensory information. Stimulus correlations can be contingent and readily available to the senses (like the temporal correlation between mouth movements and vocal sounds in speech), or can be the results of the statistical co-occurrence of certain stimulus properties that can be learnt over time (like the relation between the frequency of acoustic resonance and the size of the resonator). Over the last century, a large body of research on multisensory processing has demonstrated the existence of compatibility effects between individual features of stimuli from different sensory modalities. Such compatibility effects, termed crossmodal correspondences, possibly reflect the internalization of the natural correlation between stimulus properties.
The present dissertation assesses the effects of crossmodal correspondences on multisensory processing and reports a series of experiments demonstrating that crossmodal correspondences influence the processing rate of sensory information, distort perceptual experiences and lead to stronger multisensory integration. Moreover, a final experiment investigating the effects of contingent signals’ correlation on multisensory processing demonstrates the key role of temporal correlation in inferring whether two signals have a common physical cause or not (i.e., the correspondence problem). A Bayesian framework is proposed to interpret the present results whereby stimulus correlations, represented on the prior distribution of expected crossmodal co-occurrence, operate as cues to solve the correspondence problem.

Keywords: crossmodal correspondences
audition
vision
Multisensory integration
psychophysics
Advisor: Spence, C
Probabilistic bias in genotype-phenotype maps

Among the most fundamental features shared by all organisms is the mapping of information encoded in genotypes (genetic material) to generate phenotypes (biological structures, functions, and traits). Hence, elucidating the structure of genotype-phenotype (GP) maps is important for understanding evolution and biology.
While it is known that often GP maps are highly degenerate with many different genotypes adopting the same phenotype, the distribution of genotypes over phenotypes is less well studied. In this thesis we investigate the question of the distribution of genotypes over phenotypes, or put differently the distribution of neutral set sizes (NSS), where a neutral set is the collection of all genotypes in a GP map which map to the same phenotype. We focus on examining phenotypic bias in GP maps, where some phenotypes have disproportionally large NSS as compared to others. We find phenotypic bias to be ubiquitous in the broad range of GP maps that we analyse, from the genetic code up to molecular RNA to a model of neuronal connections, and hence we hypothesise bias to be a common property of GP maps. Further, we also consider the implications that this bias has for evolutionary outcomes, and we argue that bias is a significant influencing factor in determining evolutionary outcomes.
Finally, we propose a method to predict a phenotype's NSS via estimating the phenotype's structural complexity, without using detailed knowledge about the specifics of the relevant GP map. We achieve this via a novel application of algorithmic information theory and especially Levin's coding theorem.

Keywords: biological evolution
Probability
RNA
information theory
Advisor: Louis, A
Conspicuous silences: implicature and fictionality in the Victorian novel

This dissertation examines the central use of implicature within the Victorian novel. 'Implicature' denotes a communicative strategy in which a reader must infer the primary meaning of an utterance from that utterance's relationship to its context, rather than 'decode' explicitly presented information. While all communications rely on implicature to an extent, the novels examined in this thesis contain large gaps in their explicit narration and rely primarily on implicature to communicate central elements of their plots. If readers do not recognise these texts' implicatures, the texts will often appear incoherent: their implicatures must be acknowledged in order for the text to be understood. Because little has been said about the central role implicature can play in fictional narration, this thesis contributes to interpretations of these novels that are currently being discussed in Victorian literary scholarship, as well as literary pragmatic debates about the use of implicature within fictional texts.
The dissertation's secondary aim is to examine the implicatures which may be generated by the author's exploitation of certain reader assumptions. It focuses on the reader's potential assumption of narratorial omniscience, and relates it to the reader assumption of the narrative's fictionality. This secondary emphasis contributes to literary pragmatic conceptions of fictionality, and contributes to narratological discussions of narratorial omniscience.
Chapter One examines represented illegitimate pregnancies in Victorian novels, and illustrates implicature's use as a politeness strategy. It explains how this use of implicature is called for by the novels' fictional and Victorian contexts. Chapter Two discusses implicatures which communicate characters' semiconscious romantic desires, and relates these representations to Victorian discourses on the unconscious and narratological scholarship on consciousness representation. Chapter Three discusses the central use of implicature in sensation fiction to create narrative 'puzzles', and connects the ensuing playful, sometimes offensive tone to these implicatures' satire of the realist mode.

Keywords: implicature
Victorian literature
stylistics
pragmatics
fictionality
the novel
Advisor: Small, H
Cameron, D
Development and application of nickel stable isotopes as a new geochemical tracer

In this thesis, I have developed a new methodology for the accurate determination of mass-dependent variations in nickel (Ni) isotope compositions. Nickel is initially separated in a three-column ion-exchange procedure, and the purified solutions are analysed by multi-collector inductively coupled plasma mass spectrometry (MCICPMS) using a double-spike technique. Using this methodology, I have measured the first Ni isotope ratios for a wide variety of natural geological samples. Significant Ni isotope variations were observed, with an overall spread in delta 60Ni-values of -0.9 to 2.5 permil. In igneous rocks Ni isotopes appear to be largely homogeneous, with only small variations (0.2 permil) between different rock types. Weathering of silicate rocks does on the other hand appear to cause significant fractionation of Ni isotopes, probably producing an isotopically heavy riverine input to the ocean. A heavy isotope signature is also visible in hydrogenetic ferromanganese crusts, with surface scrapings from globally distributed crusts show an average delta 60Ni-value of 1.65 permil. However, the variation in these samples is over 1.5 permil, likely reflecting local sources or biological processes, or alternatively indicating a heterogeneous Ni isotopic composition of the ocean. Organic-rich sediments also show heavy isotopic compositions, which are possibly transferred to the crude oils originating in these types of sediments. The only significant reservoir of light Ni isotopes found during this project are sulphides from magmatic systems. Overall, this thesis demonstrates the potential of this system as a powerful new tracer for a variety of geochemical processes.

Keywords: stable isotopes
method development
geochemical applications
nickel
Advisor: Halliday, A
The strange case of the landed poor:  land reform laws, traditional San culture, and the continued poverty of South Africa’s ‡Khomani people

The ‡Khomani San people received lands in 1999 under the ‘restitution’ arm of South Africa’s land reform programme. Restitution laws, contained in the Restitution of Land Rights Act and the Communal Property Associations (‘CPA’) Act, seek not only to return lands to peoples dispossessed after 1913, but also to inculcate the ideals of South Africa’s dominant agro-pastoral-based society into defined, cohesive land-recipient ‘communities’. These ideals include centralised, hierarchical, representative, democratic leadership and decision-making structures that the West takes for granted. However, these concepts of control are not typically found among foraging or post-foraging peoples, who tend to base their societies on decentralised, small-group, egalitarian social structures that strongly oppose hierarchies, representation, or accumulation. Such social organisation remains intact even after these groups become settled or adopt non-hunting-and-gathering livelihoods, and today’s ‡Khomani self-identify as San, ‘Bushmen’, hunters, and indigenous people, despite their settlement and their adoption of varied livelihood strategies, including stock-farming. Among such groups, externally imposed governance structures tend to be viewed as illegitimate, and instead of the cohesion and order these centrally legislated structures seek to create, they instead engender dissent, conflict, and non-compliance.
The ‡Khomani, as both a formerly scattered group of apartheid-era labourers and a cultural group of San people, have struggled with little success to plan and implement ‘development’, infrastructure, and livelihood projects on their lands and have ‘failed’ to operate the Restitution and CPA Acts’ required ‘community’ land-ownership and decision-making structures successfully. Thus, restitution has failed to bring the socio-economic improvements that the new ‡Khomani lands seemed to promise. Since 2008, however, the government has temporarily taken governance and approval authority from the ‡Khomani, which has led to the creation of smaller, behind-the-scenes governing bodies, as the ‡Khomani have begun taking the reins of power in their own ways. Such bodies, including the ‡Khomani Farmers’ Association and the Bushman Raad, have begun achieving some successes on the ‡Khomani farms in part, it is argued, because they allow the ‡Khomani to reproduce the focused, non-hierarchical, small-group structures that are more suitable to them as a non-cohesive group and more culturally appropriate to them as San people. The South African government, with appropriate protections for abuse of power, should provide the space within land reform laws to allow land-recipient groups to make decisions, govern themselves, and manage their lands according to their own community realities and their own conceptions of leadership and social organisation.

Advisor: Lemon, A
Semigroup representations: An abstract approach

Chapter One After the definitions and basic results required for the rest of the thesis, a notion of spectrum for semigroup representations is introduced and some relevant examples given.
Chapter Two Any semigroup representation by isometries on a Banach space may be dilated to a group representation on a larger Banach space. A new proof of this result is presented here, and a connection is shown to exist between the dilation and the trajectories of the dual representation. The problem of dilating various types of spaces, including partially ordered spaces, C*-algebras, and reflexive spaces, is discussed, and new dilation theorems are given for dual Banach spaces and von Neumann algebras.
Chapter Three In this chapter the spectrum of a representation is examined more closely with the aid of methods from Banach algebra theory. In the case where the representation is by isometries it is shown that the spectrum is non-empty, that it is compact if and only if the representation is norm-continuous, and that any isolated point in the unitary spectrum is an eigenvalue.
Chapter Four An analytic characterisation is given of the spectral conditions that imply a representation by isometries is invertible. For representations of Z+n this con- dition is shown to be equivalent to polynomial convexity. Some topological conditions on the spectrum are also shown to imply invertibility.
Chapter Five The ideas of the previous chapters are applied to problems of asymptotic behaviour. Asymptotic stability is described in terms of the behaviour of the dual of a representation. Finally, the case when the unitary spectrum is countable is discussed in detail.

Advisor: Batty, C
Multimode absorption spectroscopy of CO and CO2 gas mixtures

The development of multimode absorption spectroscopy (MUMAS) for multi-species detec- tion and its potential for process control or environmental monitoring is reported. The simultaneous detection of CO and CO2 is demonstrated in a proof-of-principle experiment for applications in industrially relevant gas species monitoring. The technique of MUMAS is extended to the near infrared in order to detect these and other industrially relevant species.
A laser was designed and constructed to emit a multimode spectrum in the region of 1.57um to take advantage of the spectral overlap of the second vibrational overtone of CO and the combination band 3ν1 + ν3 of CO2. The laser consisted of a semi-confocal cavity employing an Er:Yb glass chip as the gain medium. The laser was pumped by a 1W laser diode at 980nm and emitted up to 30mW in a bandwidth of 180GHz. The laser emitted between 6-10 modes depending upon the selective cavity length. Mode spacings varied between 18GHz to 33GHz with an individual mode linewidth of less than 8MHz. The laser modes were simultaneously scanned using a piezo-electric transducer (PZT) in order to modulate the cavity length at frequencies between 1Hz and 10Hz.
A system for linearizing the MUMAS spectra with respect to frequency was devised based on a transmission spectra of a confocal Fabry-Perot etalon. Refinements to the MUMAS fitting code were developed to improve the computational efficiency. An initial demonstration of MUMAS on a known gas mixture of CO and CO2 was per- formed. The ratio of CO:CO2 concentrations in the gas mixture was measured with an accuracy of 0.4% which was within the supplier’s quoted uncertainty.
MUMAS is then applied to the detection of CO and CO2 concentrations in exhaust gas produced by a 1.3 litre 4-cylinder turbo-charged spark ignition engine. Relative and absolute concentrations were derived from MUMAS signals and values compared to measurements using a 4-gas analyser. Concentrations of CO and CO2 were measured using MUMAS to a precision of 0.17% and 0.23% respectively compared to less than 0.1% for the 4-gas analyser. Ratios of CO and CO2 were determined with a precision of 0.28 using MUMAS compared to 0.11 with the 4-gas analyser. The detection limit of CO was found to be 1486ppm in these circumstances.
Finally a discussion is presented of potential improvements arising from wavelength mod- ulation spectroscopy and cavity enhancement techniques.

Keywords: spectroscopy
gas sensing
exhaust gas
Advisor: Ewart, P