Ab initio calculations of group 4 metallocene reaction mechanisms: atomic layer deposition and bond activation catalysis

Thin film dielectrics based on titanium, zirconium or hafnium oxides are being introduced to increase the permittivity of insulating layers in transistors for micro/nanoelectronics and memory devices. Atomic layer deposition (ALD) is the process of choice for fabricating these films, as it allows for high control of composition and thickness in thin, conformal films which can be deposited on substrates with high aspect-ratio features. The success of this method depends crucially on the chemical properties of the precursor molecules. A successful ALD precursor should be volatile, stable in the gas-phase, but reactive on the substrate and growing surface, leading to inert by-products. In recent years, many different ALD precursors for metal oxides have been developed, but many of them suffer from low thermal stability. Much promise is shown by group 4 metal precursors that contain cyclopentadienyl (Cp = C5H5-xRx) ligands. One of the main advantages of Cp precursors is their thermal stability. In this work ab initio calculations were carried out at the level of density functional theory (DFT) on a range of heteroleptic metallocenes [M(Cp)4-n(L)n], M = Hf/Zr/Ti, L = Me and OMe, in order to find mechanistic reasons for their observed behaviour during ALD. Based on optimized monomer structures, reactivity is analyzed with respect to ligand elimination. The order in which different ligands are eliminated during ALD follows their energetics which was in agreement with experimental measurements. Titanocene-derived precursors, TiCp*(OMe)3, do not yield TiO2 films in atomic layer deposition (ALD) with water, while Ti(OMe)4 does. DFT was used to model the ALD reaction sequence and find the reason for the difference in growth behaviour. Both precursors adsorb initially via hydrogen-bonding. The simulations reveal that the Cp* ligand of TiCp*(OMe)3 lowers the Lewis acidity of the Ti centre and prevents its coordination to surface O (densification) during both of the ALD pulses. Blocking this step hindered further ALD reactions and for that reason no ALD growth is observed from TiCp*(OMe)3 and water. The thermal stability in the gas phase of Ti, Zr and Hf precursors that contain cyclopentadienyl ligands was also considered. The reaction that was found using DFT is an intramolecular α-H transfer that produces an alkylidene complex. The analysis shows that thermal stabilities of complexes of the type MCp2(CH3)2 increase down group 4 (M = Ti, Zr and Hf) due to an increase in the HOMO-LUMO band gap of the reactants, which itself increases with the electrophilicity of the metal. The reverse reaction of α-hydrogen abstraction in ZrCp2Me2 is 1,2-addition reaction of a C-H bond to a Zr=C bond. The same mechanism is investigated to determine if it operates for 1,2 addition of the tBu C-H across Hf=N in a corresponding Hf dimer complex. The aim of this work is to understand orbital interactions, how bonds break and how new bonds form, and in what state hydrogen is transferred during the reaction. Calculations reveal two synchronous and concerted electron transfers within a four-membered cyclic transition state in the plane between the cyclopentadienyl rings, one π(M=X)-to-σ(M-C) involving metal d orbitals and the other σ(C-H)-to-σ(X-H) mediating the transfer of neutral H, where X = C or N. The reaction of the hafnium dimer complex with CO that was studied for the purpose of understanding C-H bond activation has another interesting application, namely the cleavage of an N-N bond and resulting N-C bond formation. Analysis of the orbital plots reveals repulsion between the occupied orbitals on CO and the N-N unit where CO approaches along the N-N axis. The repulsions along the N-N axis are minimized by instead forming an asymmetrical intermediate in which CO first coordinates to one Hf and then to N. This breaks the symmetry of the N-N unit and the resultant mixing of MOs allows σ(NN) to be polarized, localizing electrons on the more distant N. This allowed σ(CO) and π(CO) donation to N and back-donation of π*(Hf2N2) to CO. Improved understanding of the chemistry of metal complexes can be gained from atomic-scale modelling and this provides valuable information for the design of new ALD precursors. The information gained from the model decomposition pathway can be additionally used to understand the chemistry of molecules in the ALD process as well as in catalytic systems.

Theory of elasticity and electric polarization effects in the group-III nitrides

In this work, the properties of strained tetrahedrally bonded materials are explored theoretically, with special focus on group-III nitrides. In order to do so, a multiscale approach is taken: accurate quantitative calculations of material properties are carried out in a quantum first-principles frame, for small systems. These properties are then extrapolated and empirical methods are employed to make predictions for larger systems, such as alloys or nanostructures. We focus our attention on elasticity and electric polarization in semiconductors. These quantities serve as input for the calculation of the optoelectronic properties of these systems. Regarding the methods employed, our first-principles calculations use highly- accurate density functional theory (DFT) within both standard Kohn-Sham and generalized (hybrid functional) Kohn-Sham approaches. We have developed our own empirical methods, including valence force field (VFF) and a point-dipole model for the calculation of local polarization and local polarization potential. Our local polarization model gives insight for the first time to local fluctuations of the electric polarization at an atomistic level. At the continuum level, we have studied composition-engineering optimization of nitride nanostructures for built-in electrostatic field reduction, and have developed a highly efficient hybrid analytical-numerical staggered-grid computational implementation of continuum elasticity theory, that is used to treat larger systems, such as quantum dots.

The biodiversity, control and genetic characterisation of the lactococcal 936 group phages

Phages belonging to the 936 group represent one of the most prevalent and frequently isolated phages in dairy fermentation processes using Lactococcus lactis as the primary starter culture. In recent years extensive research has been carried out to characterise this phage group at a genomic level in an effort to understand how the 936 group phages dominate this particular niche and cause regular problems during large scale milk fermentations. This thesis describes a large scale screening of industrial whey samples, leading to the isolation of forty three genetically different lactococcal phages. Using multiplex PCR, all phages were identified as members of the 936 group. The complete genome of thirty eight of these phages was determined using next generation sequencing technologies which identified several regions of divergence. These included the structural region surrounding the major tail protein, the replication region as well as the genes involved in phage DNA packing. For a number of phages the latter genomic region was found to harbour genes encoding putative orphan methyltransferases. Using small molecule real time (SMRT) sequencing and heterologous gene expression, the target motifs for several of these MTases were determined and subsequently shown to actively protect phage DNA from restriction endonuclease activity. Comparative analysis of the thirty eight phages with fifty two previously sequenced members of this group showed that the core genome consists of 28 genes, while the non-core genome was found to fluctuate irrespective of geographical location or time of isolation. This study highlights the continued need to perform large scale characterisation of the bacteriophage populations infecting industrial fermentation facilities in effort to further our understanding dairy phages and ways to control their proliferation.

The knowledge is out there

Review Essay. On Bourdieu, education and society, by Derek Robbins, Oxford, The Bardwell Press, 2006, 596 pp., £75, ISBN 0-95-486836-6. Bringing knowledge back in, from social constructivism to social realism in the sociology of education, by Michael Young, London, Routledge, 2008, 247 pp.,£23.99, ISBN 9-78-041532-121-1. Personal knowledge, towards a post-critical philosophy, by Michael Polanyi, Chicago, University of Chicago Press, 1962, 428 pp., £18.99, ISBN 0-22-667288-3.

We could make a meal out of nothing: contested explanations of inequalities in health

This paper reports on the qualitative findings from a comparative study of public health and lifestyles in South East England and Northern France, regions with similar geographic and economic characteristics. Data from health surveys showed that both countries had an increasing BMI with age, particularly in Northern France. This was despite the finding that the percentage eating fresh fruit and vegetable at least five days a week in Northern France increased with age (from well over 50% to over 90%) compared to around 50% to around 75% in South East England. Qualitative data on health inequalities and how they could be addressed were gathered by focus groups sampling from five tiers using the Townsend Index for comparability (14 in England with 106 participants overall; 13 in France with 143 participants). Both had about two thirds women participants, with a preponderance of middle aged and older people. There was a striking difference in the salience of diet between the two countries; in the French data it was raised only 14 times, whereas in England there were 165 occurrences, and these were often distinguished by their use of narrative. Older respondents contrasted the pressures on families today and the expense of fresh fruit and vegetables with their own childhood or childrearing, when cheap meals could be created using skills which have now been lost. These data therefore provide further evidence that providing food is a moral activity.

To fit in or stand out? The interaction between mortality salience, dissent and self esteem on social projection

Social projection (SP) refers to our tendency to assume that others think the same as we do, but the effect can also be used to detect the extent to which participants want to see themselves as similar to others. Simon et al (1997) found that participants informed that they were deviant increased their SP but those told that they were conformist reduced theirs. This compensatory function supports Brewer’s optimal distinctiveness which states that a balance must be struck between competing desires to feel similar and unique. In line with terror management theory, the effect was particularly apparent under conditions of mortality salience (MS). So far SP has only been examined on measures that target personal identity so this experiment developed a measure to target social identity as well. Participants were provided with either minority or majority dissent feedback, in MS or control conditions, and their SP on items relevant to personal and social identity were recorded. Results showed that group feedback only impacted upon participants SP on social identity measures and interacted with MS and self-esteem; those with high self-esteem had higher SP scores following minority dissent under conditions of mortality salience, indicating an attempt to assert their individuality. On SP measures targeting personal identity, MS and self-esteem interacted; the death prime increased SP scores for those with low self-esteem but decreased it for those with high self-esteem. Findings are interpreted in terms of TMT and optimal distinctiveness theory and their applications.

Co-evaluation as a strategy to improve working group dynamics: an experience in Sport Sciences

The aim of this study was to analyze if the perceptions of students before and after carrying out the work, that is, their perception of different aspects of the functioning of the group, the working skills acquired as well as those they think that need to be improved, varied depending on whether the contribution of the different members of the group was being co-evaluated or not. 144 students of Physical Activity and Sport Sciences participated in this study. In order to analyze the students' perception of group work the adapted questionnaire by Bourne et al. (2001) was used. Results showed that groups which implemented co-evaluation assessed more negatively the experience in general than those which did not. However, co-evaluation groups perceived their competence to work as a team had improved to a greater extent than the groups without co-evaluation, evaluating more positively both the performance and the result of work and increasing their knowledge of the other team members. Using a co-evaluation system seems to generate both a better assessment of the running of the team and the result of its work.

Electroreduction of oxygen in a series of room temperature ionic liquids composed of group 15-centered cations and anions

The electrochemical reduction of oxygen is reported in four room temperature ionic liquids (RTILs) based on quaternary alkyl -onium cations and heavily fluorinated anions in which the central atom is either nitrogen or phosphorus. Data were collected using cyclic voltammetry and potential step chronoamperometry at gold, platinum, and glassy carbon disk electrodes of micrometer dimension under water-free conditions at a controlled temperature. Analysis via fitting, to appropriate theoretical equations was then carried out to obtain kinetic and thermodynamic information pertaining to the electrochemical processes observed. In the quaternary ammonium electrolytes, reduction of oxygen was found to occur reversibly to give stable superoxide, in an analogous manner to that seen in conventional aprotic solvents such as dimethyl sufoxide and acetonitrile. The most significant difference is in the relative rate of diffusion; the diffusion coefficients of oxygen in the RTILs are an order of magnitude lower than in common organic solvents, and for superoxide these values are reduced by a further factor of 10. In the quaternary phosphonium ionic liquids, however, more complex voltammetry is observed, akin to that expected for the reduction of oxygen in acidified organic media. This is shown to be consistent with the occurrence of a proton abstraction reaction between the electrogenerated superoxide and quaternary alkyl phosphonium cations following the initial electron transfer.

Bridging the Gap between Ionic Liquids and Molten Salts: Group 1 Metal Salts of the Bistriflamide Anion in the Gas Phase

Fourier transform ion cyclotron resonance mass spectrometry experiments showed that liquid Group 1 metal salts of the bistriflamide anion undergoing reduced-pressure distillation exhibit a remarkable behavior that is in transition between that of the vapor-liquid equilibrium characteristics of aprotic ionic liquids and that of the Group 1 metal halides: the unperturbed vapors resemble those of aprotic ionic liquids, in the sense that they are essentially composed of discrete ion pairs. However, the formation of large aggregates through a succession of ion-molecule reactions is closer to what might be expected for Group I metal halides. Similar experiments were also carried out with bis{(trifluoromethyl)sulfonyl}amine to investigate the effect of H+, which despite being the smallest Group 1 cation, is generally regarded as a nonmetal species. In this case, instead of the complex ion-molecule reaction pattern found for the vapors of Group I metal salts, an equilibrium similar to those observed for aprotic ionic liquids was observed.

When does national identification lead to the rejection of immigrants? Cross-sectional and longitudinal evidence for the role of essentialist in-group definitions

Two studies were carried out in England to investigate the role of essentialist national group definitions in determining the effect of national identification on prejudice towards immigrants, and asylum seekers in particular. It was expected that the relationship between national identification and prejudice would depend on the degree to which participants endorse an essentialist (`ethnic') definition of their nationality. Consistent with this, Study 1 (N=154) found that national identification is associated with negativity towards asylum seekers only among individuals who endorse an essentialist conception of the group, and shows no significant association with prejudice among those who reject such a conception. Study 2 (N=219) used a longitudinal design conducted over 6 weeks, allowing cross-lagged analysis of causality between essentialism, identification, and behavioural intentions towards asylum seekers. A causal effect of essentialism on willingness to support a group acting against asylum seekers was observed, with no significant causal effect in the reverse direction. The reverse causal direction was observed in the case of support for a group seeking to support asylum seekers, with intended behaviours determining essentialism. The results are discussed in terms of the importance of group definitions in the study of in-group affiliations and prejudice.

Group Design-Build-Test Projects as the Core of an Integrated Curriculum in Product Design and Development

The School of Mechanical and Aerospace Engineering at Queen’s University Belfast introduced a new degree programme in Product Design and Development (PDD) in 2004. As well as setting out to meet all UK-SPEC requirements, the entirely new curriculum was developed in line with the syllabus and standards defined by the CDIO Initiative, an international collaboration of universities aiming to improve the education of engineering students. The CDIO ethos is that students are taught in the context of conceiving, designing, implementing and operating a product or system. Fundamental to this is an integrated curriculum with multiple Design-Build-Test (DBT) experiences at the core. Unlike most traditional engineering courses the PDD degree features group DBT projects in all years of the programme. The projects increase in complexity and challenge in a staged manner, with learning outcomes guided by Bloom’s taxonomy of learning domains. The integrated course structure enables the immediate application of disciplinary knowledge, gained from other modules, as well as development of professional skills and attributes in the context of the DBT activity. This has a positive impact on student engagement and the embedding of these relevant skills, identified from a stakeholder survey, has also been shown to better prepare students for professional practice. This paper will detail the methodology used in the development of the curriculum, refinements that have been made during the first five years of operation and discuss the resource and staffing issues raised in facilitating such a learning environment.

Peer Rating for Feedback in Group Projects

The National Student Survey (NSS) in the UK has since 2005 questioned final year
undergraduate students on a broad range of issues relating to their university experience.
Across disciplines and universities students have expressed least satisfaction in the areas of
assessment and feedback. In response to these results many educational practitioners have
reviewed and revised their procedures and the UK Higher Education Academy (HEA) has
produced guidelines of best practice to assist academics in improving these specific areas.
The Product Design and Development (PDD) degree at Queen’s University Belfast is
structured with an integrated curriculum with group Design Build Test (DBT) projects as the
core of each year of the undergraduate programme. Based on the CDIO syllabus and
standards the overall learning outcomes for the programme are defined and developed in a
staged manner, guided by Bloom’s taxonomy of learning domains.
Feedback in group DBT projects, especially in relation to the development of personal and
professional skills, represents a different challenge to that of individual assignment feedback.
A review of best practice was carried out to establish techniques which could be applied to
the particular context of the PDD degree without modification and also to identify areas
where a different approach would need to be applied.
A revised procedure was then developed which utilised the structure of the PDD degree to
provide a mechanism for enhanced feedback in group project work, while at the same time
increasing student development of self and peer evaluation skills. Key to this improvement
was the separation of peer ratings from assessment in the perception of the students and the
introduction of more frequent face to face feedback interviews.
This paper details the new procedures developed and additional issues which have been
raised and addressed, with reference to the published literature, during 3 years of operation.

Undecaprenyl phosphate recycling comes out of age

The recycling of the lipid carrier undecaprenyl-phosphate (Und-P) requires the dephosphorylation of Und-PP, a reaction proposed to occur at the external or periplasmic side of the bacterial cell membrane. In this issue of Molecular Microbiology, experiments based on the analysis of lipopolysaccharide modifications in Escherichia coli demonstrate that the phosphorylation of lipid A at position 1 is catalysed by the membrane enzyme LpxT (formerly YeiU). This enzyme specifically transfers the distal phosphate group from Und-PP to lipid A 1-phosphate to produce lipid A 1-diphosphate. Furthermore, this reaction requires a functionally intact MsbA protein, which catalyses the transfer of lipid A across the membrane, confirming that the LpxT-mediated lipid A modification occurs on the periplasmic side of the membrane. These observations provide a novel and unexpected link between periplasmic lipid A modifications and the Und-PP recycling pathway.

Low prevalence of primary biliary cirrhosis in Victoria, Australia. Melbourne Liver Group

A prevalence study of primary biliary cirrhosis was carried out in the state of Victoria, Australia, by means of a mail survey of specialist physicians and a review of hospital records. Eighty four cases were identified, giving a prevalence of 19.1 per million population (95% confidence limits (CI) 15.3, 23.7), which is among the lowest in published reports. The prevalence in the Australian born, at risk population (women over the age of 24) was 51 per million (95% CI 37.5, 67.9). Both these figures are considerably lower than those in populations of similar age distribution in the UK and northern Europe. Since most Victorians are descended from British or European settlers, the low prevalence of primary biliary cirrhosis in this study supports the hypothesis that local environmental factors may be important in the pathogenesis of this disease.

Perceptions of Gender Group Variability in Majority and Minority Contexts Two Field Studies with Nurses and Police Officers

Two field studies demonstrated that majority and minority size moderate perceived group variability. In Study 1 we found an outgroup homogeneity (OH) effect for female nurses in the majority, but an ingroup homogeneity (IH) effect for a token minority of male nurses. In Study 2 we found similar effects in a different setting - an OH effect for policemen in the majority and an IH effect for policewomen in the minority. Although measures of visibility, status, and, especially, familiarity tended to show the same pattern as perceived variability, there was no evidence that they mediated perceived dispersion. Results are discussed in terms of group size, rather than gender, being moderators of perceived variability, and with reference to Kanter's (1977a, 1977b) theory of group proportions.