VictorJuiz/thesis huggingface dataset:
Structure and reactivity of transition metal clusters

A range of computational and experimental techniques have been applied to the study of four metal cluster systems.
Decorated rhodium clusters RhnOm(N2O)+ (n=4−8,m=0−2) have been investigated both experimentally by IR-MPD and computationally using DFT. The effect of cluster size as well as oxygen coverage on the spectroscopy of the N2O bend are analyzed. The infrared-induced decomposition of N2O on RhnO+m is observed on all cluster sizes, with marked differences as a function of size and oxygen coverage, particularly in the case of Rh5(N2O)+.
The oxidation of CO was studied on the surface of small platinum cluster cations PtnO+m(n=3−7,m= 2,4) by IR-MPD at 400 – 2100cm−1. Spectroscopically, oxygen is found to be bound both dissociatively and molecularly on the cluster surface, while the CO band is found to red shift in cluster size, and blue shift with oxygen coverage. Oxidation of CO proceeds on all cluster sizes, with a constant branching ratio of 40% : 60% . DFT calculations identified key stationary points and barriers on the Pt4O2CO+ reaction pathway.
The one-colour Ta 2 photodissociation is studied by photoionization and VMI in the range 23500 – 24000cm−1 , finding clear evidence of a fragmentation process producing Ta , which is interpreted as fragmentation of cationic Ta+2at the two photon level. A majority of the observed channels produce either atomic (Ta(4F3/2)) or cationic (Ta+(5F1)) ground state. An improved value for the dissociation energy D0(Ta+2) is obtained, in agreement with computational predictions. The anisotropies observed show weak evidence of a perpendicular transition being involved in the photodissociation process.
Finally, the photodissociation dynamics of Cu2 are studied by spectroscopy in the range 36000 – 38200cm−1 as well as VMI. Clear evidence for resonant photolysis of Cu2 is obtained, as a result of both direct dissociation of the Cu+2 2Π ion state as well as dissociation of doubly excited Cu2 states, which leads to a determination of dimer dissociation energies. Finally, the production of Cu+2 is interpreted as evidence of photolysis of Cu3, from which a Cu3 dissociation energy is derived.

Keywords: catalysis
cluster
transition metal
Advisor: Mackenzie, S
The seeds of virtue

There is a prima facie incompatibility between a law conception of ethics, in which law concepts (e.g. ought, rule, action) are basic, and a virtue conception of ethics, in which virtue concepts (e.g. character trait, ideal, agent) are basic. However, both conceptions contain elements that are needed for an adequate ethical account. Aquinas's conception of ethics is of interest, because it combines virtue and law components within a broadly Aristotelian account. I argue that Aquinas's virtue-and-law ethical conception is not ad hoc, but emerges from, expresses, and is grounded normatively, rationally, and motivationally in his general conception of practical thought. My first objective in the thesis is to explicate and defend an interpretation of Aquinas's understanding of practical thought as the rational determination of general good into particular action. I argue, first, that this interpretation expresses Aquinas's conception of the nature of practical thought, as reflected in Aquinas's central practical concepts of order, nature, good, and reason. Second, I argue that this interpretation is expressed in Aquinas's conception of the structure of practical thought, as reflected in general, specific, and particular conceptual levels of practical thinking, reasons, and forms of reasoning. My second objective in the thesis is to show that Aquinas's virtue-and-law account presupposes and develops this conception of practical thought, and briefly to indicate how insights from Aquinas's account elucidate relationships between virtue and law ethical conceptions.
Predation and the evolution of multicellularity

The first step in the major evolutionary transition to multicellularity involves single cells forming a group. Why do cells form a group? Studies have shown that colony formation provides a benefit against predation. However, it is not well known whether this response is generic, or specific to certain prey-predator systems. We sought to assess this by measuring colony formation in nine 'algal-putative predator' combinations; the Chlorophyte algae Chlorella vulgaris, Chlorella sorokiniana and Scenedesmus obliquus as prey, and the flagellate Ochromonas spp., the ciliate Tetrahymena thermophila and the crustacean Daphnia magna as putative predators. We found that colony formation is a generic response of the algae C. sorokiniana, C. vulgaris and S. obliquus to predation by Ochromonas spp., T. thermophila or D. magna. Notably, the algae formed colonies regardless of whether the putative predator grazed upon the algae, indicating that predation by itself is not always a prerequisite for colony formation, but this response may have evolved in the algae as a defensive mechanism against potential predation. In six combinations, colonies could not be ingested by the predator, suggesting that colonies have a 'size benefit' against predation. These results outline the importance of predation as a generic factor driving colony formation and help enhance our understanding of the benefits and costs involved in colony formation, the first step in the evolution of multicellularity.

Keywords: group size
Chlorophyceae
group formation
induced defense
multicellularity
Advisor: West, S
Supramolecular control of synthesis and electronic structure of porphyrin oligomers

The work described in this thesis demonstrates the use of supramolecular chemistry in the template-directed synthesis of porphyrin nanorings and as a tool to control conformation and topology of π-conjugated porphyrin oligomers. Particular emphasis is placed on changes to the electronic structure of these oligomers depending on their conformation.
Chapter 1 gives an overview of π-conjugated porphyrin oligomers and conjugated macrocycles in general, followed by an introduction into supramolecular cooperativity and small angle X-ray scattering in solution.
Chapter 2 describes advances in the synthesis, solution structure elucidation and optoelectronic properties of a fully conjugated cyclic porphyrin hexamer. The high rigidity and symmetry of this nanoring as well as its bent π-system lead to a significant decrease in its HOMO-LUMO gap. The resulting near-infrared emission was exploited in the fabrication of light emitting diodes, demonstrating the use of a bent topology for minimizing aggregation in thin films.
The synthesis of a [12]porphyrin nanoring using a hexadentate template is presented in Chapter 3. The concept of Vernier templating is introduced as a general strategy for the synthesis of large monodisperse macrocycles. The nanoring is characterized and its cooperative binding to two template molecules is studied. In Chapter 4 a bidentate ligand is used in the cooperative formation of a sandwich complex beween two nanorings.
Chapter 5 provides an analysis of the rigidity of the butadiyne linked porphyrin oligomers used throughout this thesis. A linear chain is significantly more flexible in solution than on a surface where it is confined within two dimensions. Analysis of the persistence length indicates that a porphyrin nanoring with more than around 20 units would not be significantly strained.
The supramolecular binding of linear porphyrin oligomers to carbon nanotubes is analyzed in Chapter 6. The binding strength increases sharply with oligomer length and binding is strongest with (8,6) and (7,5) tubes. The energy level alignment in these porphyrin CNT complexes appears to be favorable for an application in photovoltaics.
In Chapter 7 bisamidine-carboxylate salt bridges together with zinc-nitrogen coordination chemistry are used to access a variety of topologies in assemblies based on carboxylic acid functionalized porphyrin dimers.

Keywords: Self-Assembly
pi-Conjugation
OLED
SAXS
Template
Porphyrin
Supramolecular Cooperativity
Advisor: Anderson, H
A framework for processing correlated probabilistic data

The amount of digitally-born data has surged in recent years. In many scenarios, this data is inherently uncertain (or: probabilistic), such as data originating from sensor networks, image and voice recognition, location detection, and automated web data extraction. Probabilistic data requires novel and different approaches to data mining and analysis, which explicitly account for the uncertainty and the correlations therein.
This thesis introduces ENFrame: a framework for processing and mining correlated probabilistic data. Using this framework, it is possible to express both traditional and novel algorithms for data analysis in a special user language, without having to explicitly address the uncertainty of the data on which the algorithms operate. The framework will subsequently execute the algorithm on the probabilistic input, and perform exact or approximate parallel probability computation. During the probability computation, correlations and provenance are succinctly encoded using probabilistic events.
This thesis contains novel contributions in several directions. An expressive user language – a subset of Python – is introduced, which allows a programmer to implement algorithms for probabilistic data without requiring knowledge of the underlying probabilistic model. Furthermore, an event language is presented, which is used for the probabilistic interpretation of the user program. The event language can succinctly encode arbitrary correlations using events, which are the probabilistic counterparts of deterministic user program variables. These highly interconnected events are stored in an event network, a probabilistic interpretation of the original user program. Multiple techniques for exact and approximate probability computation (with error guarantees) of such event networks are presented, as well as techniques for parallel computation.
Adaptations of multiple existing data mining algorithms are shown to work in the framework, and are subsequently subjected to an extensive experimental evaluation. Additionally, a use-case is presented in which a probabilistic adaptation of a clustering algorithm is used to predict faults in energy distribution networks. Lastly, this thesis presents techniques for integrating a number of different probabilistic data formalisms for use in this framework and in other applications.

Keywords: uncertain data
clustering
classification
correlations
probability computation
data mining
machine learning
probabilistic data
ENFrame
Advisor: Olteanu, D
Poverty dynamics: childhood experience on a low income

The UK government has pledged to end child poverty by 2020. It is not known how far the measure of child poverty used by the government corresponds to differences in children’s experiences. Qualitative research on poverty has not generally been informed by the insights of dynamic research, which investigates duration, timing and transitions, among other temporal topics. Qualitative and quantitative methods have not generally been combined in social policy research on poverty, which limits the explanatory power of both. The thesis presents an analysis of the correspondence or lack of correspondence between qualitative and quantitative research on child poverty as a temporal experience.
Semi-structured life history interviews were conducted with 15-21 year olds in Britain with experience of child poverty in the period 1997-2001. These were analysed alongside secondary analysis of the British Household Panel Survey (1991-2005). The qualitative respondents lived in households which took part in the survey, so there is a direct link between the two methods.
The assumptions, methods and findings of dynamic poverty research are in general found to be a simplified and decontexualised version, rather than a misrepresentation of, the qualitative findings. Time formed an important part of the experience of poverty for children. It was not possible to fully match together exits from poverty with perceived improvements in circumstances, and entries into poverty with perceived deteriorations in circumstances, though this was partly due to limited recall and lack of contemporaneous knowledge. Nor were these changes clearly placed in time by respondents, in terms of duration and timing. Although most respondents did not explicitly engage with the idea of poverty as a personal experience, poverty-like accounts of disadvantage and difference were found in the accounts of all respondents. Thus, there is evidence for and against the way child poverty is currently measured.

Keywords: British Household Panel Survey
quantitative
qualitative
child poverty
Advisor: Walker, R
Structural studies of a membrane embedded chloride channel from E.Coli, a prokaryotic homologue of ClC channels

The ClC family of chloride channels are found throughout the eukaryotes and homologues are found among the prokaryotes. There are nine ClC chloride channels found in mammals that are expressed either ubiquitously or in specific tissues. They have a role in a broad spectrum of cellular functions, ranging from the control of electrical excitability of neurons and the maintenance of the balance of charge required in the acidification of organelles, to the regulation of cell volume. The physiological importance of these channels is often demonstrated by disease causing mutations. Mutations in ClC chloride channels cause myotonias, Becker’s Disease and have been implicated in the spread of cancer. The structural information on members of the ClC family is extremely limited. For this reason ClC prokaryotic homologues, ecClC1 and ecClC2 from E.coli, were cloned and expressed in the hope that this system would produce sufficient amounts of protein to grow crystals in order to obtain three-dimensional information. This information will provide a detailed mechanism of chloride conduction and molecular architecture of the channel necessary for the further physiological and pharmacological characterisation of this important family of chloride channels. The E.coli ClC chloride channel ecClC was cloned from E.coli genomic DNA and overexpressed in E.coli. The recombinant protein was purified from the E.coli membranes using detergents. Metal affinity and size exclusion chromatography were used to purify the protein to near homogeneity. Crystals of ecClC2 have been grown that diffract to 4Å and structural analysis is underway. This thesis describes the development of the purification protocol, the crystallisation of the protein and the preliminary analysis of the X-ray diffraction data.

Keywords: prokaryote
ion channel
CLC
purification
Chloride channel
membrane protein
X-ray crystallography
structure
Advisor: Doyle, D
A REST model for high throughput scheduling in computational grids

Current grid computing architectures have been based on cluster management and batch queuing systems, extended to a distributed, federated domain. These have shown shortcomings in terms of scalability, stability, and modularity. To address these problems, this dissertation applies architectural styles from the Internet and Web to the domain of generic computational grids. Using the REST style, a flexible model for grid resource interaction is developed which removes the need for any centralised services or specific protocols, thereby allowing a range of implementations and layering of further functionality. The context for resource interaction is a generalisation and formalisation of the Condor ClassAd match-making mechanism. This set theoretic model is described in depth, including the advantages and features which it realises. This RESTful style is also motivated by operational experience with existing grid infrastructures, and the design, operation, and performance of a proto-RESTful grid middleware package named DIRAC. This package was designed to provide for the LHCb particle physics experiment’s “off-line” computational infrastructure, and was first exercised during a 6 month data challenge which utilised over 670 years of CPU time and produced 98 TB of data through 300,000 tasks executed at computing centres around the world. The design of DIRAC and performance measures from the data challenge are reported. The main contribution of this work is the development of a REST model for grid resource interaction. In particular, it allows resource templating for scheduling queues which provide a novel distributed and scalable approach to resource scheduling on the grid.

Keywords: computational science
scheduling
grid computing
Advisor: McArthur, I
McKeever, S
Technological change and growth dynamics

In this work we investigate the sources and growth effects of technological innovation in UK industries over the years 1966-1993. Our main finding is that technological activities are always beneficial to labour productivity growth and normally also beneficial to employment growth. Moreover, it is possible to aggregate industries into fairly stable technological clusters, and the main sources of innovation change broadly in accordance with the technological characterisation of the industry. We also analyse the effect of inter-industry demand transmissions on employment share dynamics, and find that these effects are generally important. However, demand expansions in customer industries do not always imply expanding employment shares in supplying industries, and we did not find any evident linkage between the sign of the demand effect and the technological characterisation of industries. Testing the models developed to fit observed changes in labour productivity and employment shares over the periods 1974-79 and 1979-91, we find that growth dynamics over the period 1974-79 have been more related to technological change than over the period 1979-91. In particular, pure capital deepening has been one of the main engines of growth over the period 1979-91.

Advisor: Nickell, S
Inflation expectations, labour markets and EMU

This thesis examines the measurement, applications and properties of consumer inflation expectations in the context of eight European Union countries: France, Germany, the UK, Spain, Italy, Belgium, the Netherlands and Sweden.
The data proceed mainly from the European Commission's Consumer Survey and are qualitative in nature, therefore requiring quantification prior to use. This study first seeks to determine the optimal quantification methodology among a set of approaches spanning three traditions, associated with Carlson-Parkin (1975), Pesaran (1984) and Seitz (1988). The success of a quantification methodology is assessed on the basis of its ability to match quantitative expectations data and on its behaviour in an important economic application, namely the modelling of wages for our sample countries. The wage equation developed here draws on the theoretical background of the staggered contracts and the wage bargaining literature, and controls carefully for inflation expectations and institutional variables. The Carlson-Parkin variation proposed in Curto Millet (2004) was found to be the most satisfactory. This being established, the wage equations are used to test the hypothesis that the advent of EMU generated an increase in labour market flexibility, which would be reflected in structural breaks. The hypothesis is essentially rejected. Finally, the properties of inflation expectations and perceptions themselves are examined, especially in the context of EMU. Both the rational expectations and rational perceptions hypotheses are rejected. Popular expectations mechanisms, such as the "rule-of-thumb" model or Akerlof et al.'s (2000) "near-rationality hypothesis" are similarly unsupported. On the other hand, evidence is found for the transmission of expert forecasts to consumer expectations in the case of the UK, as in Carroll's (2003) model. The distribution of consumer expectations and perceptions is also considered, showing a tendency for gradual (as in Mankiw and Reis, 2002) but non-rational adjustment. Expectations formation is further shown to have important qualitative features.

Keywords: labour market institutions
time series
credibility
central banks
flexibility
nonwage labor costs
expert forecasts
wage differentials
wage level
unemployment
competitiveness
expectations
labor markets
equilibrium correction models
compensation
productivity
inflation
distribution
survey data
exchange rate mechanism
policy coordination
inflation expectations
wages
euro
econometric modeling
public policy
collective bargaining
consumers
perceptions
inflation targeting
Phillips curve
Europe
EMU
forecasting
trade unions
policy design
benefits
applied econometrics
rationality
European Monetary Union
inflation perceptions
macroeconomics
institutions
survey methods
unions
labour markets
European Union
expectations distribution
monetary policy
wage equations
labor costs
quantification
deflation
prices
Advisor: Muellbauer, J
Accommodating the public interest in international investment treaties: police powers, expropriation and treaty interpretation

This MPhil thesis analyses the extent to which customary international law principles that protect the right of States to regulate in the public interest are accommodated within international investment treaties (IITs). The thesis focuses on the police powers doctrine, which acknowledges that States have the right to enact reasonable, non-discriminatory regulation that is aimed at the public interest and enacted in accordance with good faith and due process. Such regulation will not constitute an expropriation. The thesis explores the concept of 'police power', articulates the police powers doctrine and situates the doctrine within customary international law.
The thesis then examines how the police powers doctrine can be accommodated within IITs using the principles of treaty interpretation in the Vienna Convention on the Law of Treaties (VCLT). The police powers doctrine may be 'accommodated' in two ways: first, pursuant to Article 31(1) VCLT, by looking to the ordinary meaning of 'expropriation', and secondly via Article 31(3)(c) VCLT, which allows the police powers doctrine to be taken into account as a relevant rule of international law applicable between the parties. This approach is contrasted with the interpretation of annexures included in recent IITs, concluding that it is unlikely that these annexures provide greater accommodation than the proper application of the VCLT.
The conclusion of this thesis is that the principles of treaty interpretation allow the police powers doctrine to be considered when determining the meaning of an expropriation provision in an IIT. To this extent, the public interest is accommodated in IITs.

Keywords: Customary International Law
International Investment Law
Police Powers
Treaty Interpretation
Advisor: Akande, D