Understanding the electronic structure of LiFePO4 and FePO4

This thesis has detailed the extensive analysis of the XAS and RIXS spectra of LiFePO4 and FePO4, with the primary focus on LiFePO4. One of the primary motivations for this study was to understand the electronic structure of the two compounds and, in particular, shed some light on the nature of electron correlation within the samples. Two classes of band structure calculations have come to light. One solution uses the Hubbard U parameter, and this solution exhibits a band gap of about 4 eV. Other solutions that use standard DFT electron correlation functionals yield band gaps between 0 and 1.0 eV. The RIXS spectra of LiFePO4 and FePO4 were analyzed using Voigt function fitting, an uncommon practice for RIXS spectra. Each of the spectra was fit to a series of Voigt functions in an attempt to localize the peaks within the spectra. These peaks were determined to be RIXS events, and the energetic centers of these peaks were compared to a small band gap band structure calculation. The results of the RIXS analysis strongly indicate that the small gap solution is correct. This was a surprising result, given that LiFePO4 is an ionic, insulating transition metal oxide, showing all of the usual traits of a Mott-type insulator. This contradiction was explained in terms of polaron formation. Polarons can severely distort the lattice, which changes the local charge density. This changes the local DOS such that the DOS probed by XAS or RIXS experiments is not necessarily in the ground state. In particular, polaron formation can reduce the band gap. Thus, the agreement between the small gap solution and experiment is false, in the sense that the physical assumptions that formed the basis of the small gap calculations do not reflect reality. Polaronic distortion was also tentatively put forward as an explanation for the discrepancy between partial fluorescence yield, total fluorescence yield, and total electron yield measurements of the XAS spectra of LiFePO4 and FePO4

The many mysteries of graphene oxide

Graphene, the first two-dimensional crystal ever found, is a material that has attracted fervent and sustained interest from condensed matter researchers from around the world. It has a unique and unprecedented band structure in a bulk material: the bands near the Fermi level are linear, leading to massless charge carriers that propagate at the speed of light. However, graphene does not possess a band gap, and as such, it cannot be used to process information in any electronic device that uses digital logic. Graphene is oxidized when several different basic functional groups like hydroxyls, carboxyls, and epoxides bond to the hexagonal carbon basal plane to make graphene oxide (GO). The result is a nonstoichiometric and highly disordered system that, according to the results shown in this thesis, consists of zones of densely-packed functional groups interspersed between zones of relatively small functional group concentration. This has been confirmed by DFT calculations presented here, which is the first time that a successful simulation of the GO density of states has been compared to X-ray data. Contrary to many assumptions in the literature, many of the features in the density of states of GO are due not to carbon sites bonded to functional groups, but are due to nearby non-functionalized carbon sites. The band gap of graphene oxide is principally controlled by oxidation level. Reduction, followed by heating, will regenerate the near-Fermi states and close the band gap significantly as has been seen by others. However, heating non-reduced graphene oxide can also result in a much-reduced band gap, which occurs because intercalated water can react with the heated GO sample to remove functional groups by creation and eventual expulsion of carbon dioxide. The band gap of GO is further complicated by stacking effects if it is multilayered, because residual pi-conjugated states in neighboring planes interact. The two major types of stacking in graphite are AA-stacking and AB-stacking. AA-stacking interactions cause the pi * resonance to broaden and push states to lower energy, which means that AA-stacking determines the width of the gap in highly oxidized samples. However, direct oxidation of graphene is not the only way that one alter the electronic structure of GO. Other results presented here also show that non-covalent functionalization of graphene oxide by amorphous solid water is a powerful, reversible way to dramatically change the GO electronic structure

The time course of attentional and oculomotor capture reveals a common cause

Eye movements are often misdirected toward a distractor when it appears abruptly, an effect known as oculomotor capture. Fundamental differences between eye movements and attention have led to questions about the relationship of oculomotor capture to the more general effect of sudden onsets on performance, known as attentional capture. This study explores that issue by examining the time course of eye movements and manual localization responses to targets in the presence of sudden-onset distractors. The results demonstrate that for both response types, the proportion of trials on which responses are erroneously directed to sudden onsets reflects the quality of information about the visual display at a given point in time. Oculomotor capture appears to be a specific instance of a more general attentional capture effect. Differences and similarities between the two types of capture can be explained by the critical idea that the quality of information about a visual display changes over time and that different response systems tend to access this information at different moments in time

Specialised minds: extending adaptive explanations of personality to the evolution of psychopathology

Traditional evolutionary theory invoked natural and sexual selection to explain species- and sex-typical traits. However, some heritable inter-individual variability in behaviour and psychology – personality – is probably adaptive. Here we extend this insight to common psychopathological traits. Reviewing key findings from three background areas of importance – theoretical models, non-human personality and evolved human social dynamics – we propose that a combination of social niche specialisation, negative frequency-dependency, balancing selection and adaptive developmental plasticity should explain adaptation for individual differences in psychology – ‘specialised minds’ – explaining some variance in personality and psychopathology trait dimensions, which share various characteristics. We suggest that anthropological research of behavioural differences should be extended past broad demographic factors (age and sex) to include individual specialisations. As a first step towards grounding psychopathology in ancestral social structure, we propose a minimum plausible prevalence, given likely ancestral group sizes, for negatively frequency-dependent phenotypes to be maintained as specialised tails of adaptive distributions – below the calculated prevalence, specialisation is highly unlikely. For instance, chronic highly debilitating forms of autism or schizophrenia are too rare for such explanations, whereas attention-deficit-hyperactivity disorder and broad autism phenotypes are common enough to have existed in most hunter-gatherer bands, making adaptive explanations more plausible

Nasal respiration is necessary for ketamine-dependent high frequency network oscillations and behavioral hyperactivity in rats

Changes in oscillatory activity are widely reported after subanesthetic ketamine, however their mechanisms of generation are unclear. Here, we tested the hypothesis that nasal respiration underlies the emergence of high-frequency oscillations (130–180 Hz, HFO) and behavioral activation after ketamine in freely moving rats. We found ketamine 20 mg/kg provoked “fast” theta sniffing in rodents which correlated with increased locomotor activity and HFO power in the OB. Bursts of ketamine-dependent HFO were coupled to “fast” theta frequency sniffing. Theta coupling of HFO bursts were also found in the prefrontal cortex and ventral striatum which, although of smaller amplitude, were coherent with OB activity. Haloperidol 1 mg/kg pretreatment prevented ketamine-dependent increases in fast sniffing and instead HFO coupling to slower basal respiration. Consistent with ketamine-dependent HFO being driven by nasal respiration, unilateral naris blockade led to an ipsilateral reduction in ketamine-dependent HFO power compared to the control side. Bilateral nares blockade reduced ketamine-induced hyperactivity and HFO power and frequency. These findings suggest that nasal airflow entrains ketamine-dependent HFO in diverse brain regions, and that the OB plays an important role in the broadcast of this rhythm

An Antidote to Overpathologizing Computer-Mediated Communication: An Evolutionary Perspective on Mixed Effects of Mismatch

Mixed associations are recurrently found between computer-mediated communication (CMC) and mental health & well-being. Recently, different theoretical efforts have emerged to parse these mixed results. However, evolutionary considerations in such efforts remain largely on the periphery, despite fields like evolutionary medicine and anthropology often theorising about mental health problems arising due to evolutionarily novel environmental circumstances: so-called evolutionary mismatch. While certain aspects of CMC have been previously identified as plausible evolutionary mismatches, two important limitations emerge: (a) a failure to contextualise the negative mental health effects of CMC against other broader societal factors which are plausible pre-existing evolutionary mismatches themselves; (b) ignoring the positive effects of CMC in mitigating these mismatches. In this paper, we propose an evolutionary perspective that addresses these two limitations while noting distinct epistemic and empirical benefits of such a perspective (e.g. providing a culturally invariant theory-driven baseline of ‘normal behaviour’, renewed theoretical focus on alternative variables, concrete design recommendations). Importantly, we contend that our perspective serves as an antidote to the overpathologisation of novel behaviours facilitated by CMC by framing such behaviours within the hunter-gatherer social environment characterising the majority of our evolutionary history

Application of acidogenic solids removal in the biological treatment of wastewater from a Bagasse based pulp and paper mill

No abstract available.Dissertation (MSc (Water Utilization))--University of Pretoria, 2006.Chemical Engineeringunrestricte

Layering in peralkaline magmas, Ilímaussaq Complex, S Greenland

EJH acknowledges funding from a NERC PhD studentship and the work was completed at the University of St Andrews, UK.The peralkaline to agpaitic Ilímaussaq Complex, S. Greenland, displays spectacular macrorhythmic (> 5 m) layering via the kakortokite (agpaitic nepheline syenite), which outcrops as the lowest exposed rocks in the complex. This study applies crystal size distribution (CSD) analyses and eudialyte-group mineral chemical compositions to study the marker horizon, Unit 0, and the contact to the underlying Unit − 1. Unit 0 is the best-developed unit in the kakortokites and as such is ideal for gaining insight into processes of crystal formation and growth within the layered kakortokite. The findings are consistent with a model whereby the bulk of the black and red layers developed through in situ crystallisation at the crystal mush–magma interface, whereas the white layer developed through a range of processes operating throughout the magma chamber, including density segregation (gravitational settling and flotation). Primary textures were modified through late-stage textural coarsening via grain overgrowth. An open-system model is proposed, where varying concentrations of halogens, in combination with undercooling, controlled crystal nucleation and growth to form Unit 0. Our observations suggest that the model is applicable more widely to the layering throughout the kakortokite series and potentially other layered peralkaline/agpaitic rocks around the world.Publisher PDFPeer reviewe