DFT-Based Study of the First PCET of the OER on Large (001)-Exposing Anatase TiO2 Nanoparticles in a Water-Splitting Environment

This dissertation computationally studies the oxygen evolution reaction (OER) that occurs at the surface of titanium dioxide (TiO2) nanoparticles in water, specifically the first proton-couple electron transfer (PCET) of four sequential PCETs that the overall OER comprises. To do so, we first modelled TiO¬2 nanoparticles and developed a realistic passivation scheme for the nanoparticle’s surface in an aqueous environment. Additionally, we developed a fragment-based initial guess (FIG) methodology in order to make studying systems approaching real-life nanoparticle sizes computationally tenable. The FIG methodology allowed us to employ hybrid-DFT (B3LYP) calculations to study systems of around 5000 basis functions, or more than 500 atoms. Then, we simulated the PCET by selecting particular points along the PCET reactant pathway and optimizing the system at each of these dozen points. In order to make these optimizations occur in a tractable amount of time, they were run on the STAMPEDE supercomputer operated by the Texas Advanced Computing Center (TACC), implemented with an OpenMP/MPI hybrid parallelization. These optimizations provided us with a picture of the electronic structure changes that occur over the course of the PCET and allowed us to calculate theoretical overpotentials to the PCET, both of which inform our conclusion of the nature of the inefficiency of the solar water-splitting reaction. In short, our studies show the major source of inefficiency to be the thermodynamic instability of the intermediate oxygen species (a hydroxyl adsorbate) on the surface of the nanoparticle. Additionally, while the hole created by cationization does lower the overpotential of the PCET, we do not find that this is because the two happen concertedly, which would confer stability to the system and lower the total energy, but rather for some other reason. Additionally, we do not find that the hole gets filled by the transferring electron of the PCET, raising questions as to how the OER can continue to occur without the structure of the nanoparticle degrading

Structure and Homology of <i>Psittacosaurus </i>Tail Bristles

We examined bristle-like appendages on the tail of the Early Cretaceous basal ceratopsian dinosaur Psittacosaurus with laser-stimulated fluorescence imaging. Our study reveals previously unknown details of these structures and confirms their identification as integumentary appendages. For the first time, we show that most bristles appear to be arranged in bundles and that they exhibit a pulp that widens towards the bristle base. We consider it likely that the psittacosaur bristles are structurally and developmentally homologous to similar filamentous appendages of other dinosaurs, namely the basal heterodontosaurid Tianyulong and the basal therizinosauroid theropod Beipiaosaurus, and attribute the greater robustness of the bristles of Psittacosaurus to a higher degree of cornification and calcification of its integument (both skin and bristles). Although the psittacosaur bristles are probably homologous with avian feathers in their origin from discrete cell populations, it is uncertain whether they developed from a follicle, one of the developmental hallmarks of true feathers. In particular, we note a striking resemblance between the psittacosaur bristles and the cornified spine on the head of the horned screamer, Anhima cornuta, an extant anseriform bird. Similar, albeit thinner keratinous filaments of extant birds are the ‘beard’ of the turkey, Meleagris gallopavo, and the crown of the Congo peafowl, Afropavo congensis. All of these structures of extant birds are distinct from true feathers, and because at least the turkey beard does not develop from follicles, detailed future studies of their development would be invaluable towards deepening our understanding of dinosaur filamentous integumentary structures

Copy number variations and risk for schizophrenia in 22q11.2 deletion syndrome

22q11.2 Deletion Syndrome (22q11.2DS) is a common microdeletion syndrome with congenital and late-onset features. Testing for the genomic content of copy number variations (CNVs) may help elucidate the 22q11.2 deletion mechanism and the variable clinical expression of the syndrome including the high (25%) risk for schizophrenia. We used genome-wide microarrays to assess CNV content and the parental origin of 22q11.2 deletions in a cohort of 100 adults with 22q11.2DS (44 with schizophrenia) and controls. 22q11.2DS subjects with schizophrenia failed to exhibit de novo CNVs or any excess of novel inherited CNVs outside the 22q11.2 region. There were no significant effects of parental origin of the 22q11.2 deletion, deletion length, parental age or family history on expression of schizophrenia. There was no evidence for a general increase of de novo CNVs in 22q11.2DS. A novel finding was the relative paucity of males with de novo 22q11.2 deletions of paternal origin (P = 0.019). The Y chromosome may play a mediating role in the mechanism of 22q11.2 deletion events during spermatogenesis, resulting in the previously observed excess of maternal de novo 22q11.2 deletions. Hemizygosity of the 22q11.2 region appears to be the major CNV-related risk factor for schizophrenia in 22q11.2DS. The results reinforce the need for further efforts to identify specific molecular mechanisms underlying this expression and to identify the 1% of patients with schizophrenia who carry 22q11.2 deletions

Differential branching fraction and angular analysis of the decay B0→K∗0μ+μ−

The angular distribution and differential branching fraction of the decay B 0→ K ∗0 μ + μ − are studied using a data sample, collected by the LHCb experiment in pp collisions at s√=7 TeV, corresponding to an integrated luminosity of 1.0 fb−1. Several angular observables are measured in bins of the dimuon invariant mass squared, q 2. A first measurement of the zero-crossing point of the forward-backward asymmetry of the dimuon system is also presented. The zero-crossing point is measured to be q20=4.9±0.9GeV2/c4 , where the uncertainty is the sum of statistical and systematic uncertainties. The results are consistent with the Standard Model predictions

Opposite-side flavour tagging of B mesons at the LHCb experiment

The calibration and performance of the oppositeside flavour tagging algorithms used for the measurements of time-dependent asymmetries at the LHCb experiment are described. The algorithms have been developed using simulated events and optimized and calibrated with B + →J/ψK +, B0 →J/ψK ∗0 and B0 →D ∗− μ + νμ decay modes with 0.37 fb−1 of data collected in pp collisions at √ s = 7 TeV during the 2011 physics run. The oppositeside tagging power is determined in the B + → J/ψK + channel to be (2.10 ± 0.08 ± 0.24) %, where the first uncertainty is statistical and the second is systematic

Measurement of the Bs0→J/ψKS0B_s^0\to J/\psi K_S^0 branching fraction

The $B_s^0\to J/\psi K_S^0$ branching fraction is measured in a data sample corresponding to 0.41$fb^{-1}$ of integrated luminosity collected with the LHCb detector at the LHC. This channel is sensitive to the penguin contributions affecting the sin2$\beta$ measurement from $B^0\to J/\psi K_S^0$ The time-integrated branching fraction is measured to be $BF(B_s^0\to J/\psi K_S^0)=(1.83\pm0.28)\times10^{-5}$. This is the most precise measurement to date

Search for CP violation in D+→ϕπ+ and D+s→K0Sπ+ decays

A search for CP violation in D + → ϕπ + decays is performed using data collected in 2011 by the LHCb experiment corresponding to an integrated luminosity of 1.0 fb−1 at a centre of mass energy of 7 TeV. The CP -violating asymmetry is measured to be (−0.04 ± 0.14 ± 0.14)% for candidates with K − K + mass within 20 MeV/c 2 of the ϕ meson mass. A search for a CP -violating asymmetry that varies across the ϕ mass region of the D + → K − K + π + Dalitz plot is also performed, and no evidence for CP violation is found. In addition, the CP asymmetry in the D+s→K0Sπ+ decay is measured to be (0.61 ± 0.83 ± 0.14)%

Model-independent search for CP violation in D0→K−K+π−π+ and D0→π−π+π+π− decays

A search for CP violation in the phase-space structures of D0 and View the MathML source decays to the final states K−K+π−π+ and π−π+π+π− is presented. The search is carried out with a data set corresponding to an integrated luminosity of 1.0 fb−1 collected in 2011 by the LHCb experiment in pp collisions at a centre-of-mass energy of 7 TeV. For the K−K+π−π+ final state, the four-body phase space is divided into 32 bins, each bin with approximately 1800 decays. The p-value under the hypothesis of no CP violation is 9.1%, and in no bin is a CP asymmetry greater than 6.5% observed. The phase space of the π−π+π+π− final state is partitioned into 128 bins, each bin with approximately 2500 decays. The p-value under the hypothesis of no CP violation is 41%, and in no bin is a CP asymmetry greater than 5.5% observed. All results are consistent with the hypothesis of no CP violation at the current sensitivity

Measurement of the CP-violating phase \phi s in Bs->J/\psi\pi+\pi- decays

Measurement of the mixing-induced CP-violating phase phi_s in Bs decays is of prime importance in probing new physics. Here 7421 +/- 105 signal events from the dominantly CP-odd final state J/\psi pi+ pi- are selected in 1/fb of pp collision data collected at sqrt{s} = 7 TeV with the LHCb detector. A time-dependent fit to the data yields a value of phi_s=-0.019^{+0.173+0.004}_{-0.174-0.003} rad, consistent with the Standard Model expectation. No evidence of direct CP violation is found.Comment: 15 pages, 10 figures; minor revisions on May 23, 201