Structure and Properties of Bi-containing Mixed A-site Perovskites

This thesis describes a series of studies undertaken to explore the criteria for the stabilization of Bi3+ in a perovskite through the formation of mixed A-site solid solutions. Electronically similar to Pb2+ but with a smaller ionic radius, Bi3+ has the potential to replace and improve upon Pb-based counterparts for dielectric and piezoelectric applications. Building off the discovery that Bi(Zn1/2Ti1/2)O3 increases the tetragonality of PbTiO3, the first part of this work identified a new substituent, Bi(Zn3/4W1/4)O6, that is also able to increase the c/a of PbTiO3. In the process, the crystal chemical criterion for enhancing the tetragonality of PbTiO3 was clarified. From there, these tetragonality-enhancing additives were introduced into lead-free perovskite chemistries in an attempt to stabilize a new generation of environmentally benign ferroelectric materials. The final section returns to lead-containing systems by investigating ternary systems in an attempt to capture the high c/a of the mixed Pb-Bi systems at an MPB. Unexpected dielectric behavior was observed in some compositions, which was shown to be the result of the structure entering a region of 2-phase coexistence. A new crystal-chemical parameter is defined to describe the variance of the B-site displacement factors and used to develop an empirical model for predicting the incidence of this 2-phase coexistence region. An atomistic model similar to those of relaxor ferroelectrics was proposed to explain the behavior

Preprocessing Solar Images while Preserving their Latent Structure

Telescopes such as the Atmospheric Imaging Assembly aboard the Solar Dynamics Observatory, a NASA satellite, collect massive streams of high resolution images of the Sun through multiple wavelength filters. Reconstructing pixel-by-pixel thermal properties based on these images can be framed as an ill-posed inverse problem with Poisson noise, but this reconstruction is computationally expensive and there is disagreement among researchers about what regularization or prior assumptions are most appropriate. This article presents an image segmentation framework for preprocessing such images in order to reduce the data volume while preserving as much thermal information as possible for later downstream analyses. The resulting segmented images reflect thermal properties but do not depend on solving the ill-posed inverse problem. This allows users to avoid the Poisson inverse problem altogether or to tackle it on each of $\sim$10 segments rather than on each of $\sim$10$^7$ pixels, reducing computing time by a factor of $\sim$10$^6$. We employ a parametric class of dissimilarities that can be expressed as cosine dissimilarity functions or Hellinger distances between nonlinearly transformed vectors of multi-passband observations in each pixel. We develop a decision theoretic framework for choosing the dissimilarity that minimizes the expected loss that arises when estimating identifiable thermal properties based on segmented images rather than on a pixel-by-pixel basis. We also examine the efficacy of different dissimilarities for recovering clusters in the underlying thermal properties. The expected losses are computed under scientifically motivated prior distributions. Two simulation studies guide our choices of dissimilarity function. We illustrate our method by segmenting images of a coronal hole observed on 26 February 2015

Detecting Unspecified Structure in Low-Count Images

Unexpected structure in images of astronomical sources often presents itself upon visual inspection of the image, but such apparent structure may either correspond to true features in the source or be due to noise in the data. This paper presents a method for testing whether inferred structure in an image with Poisson noise represents a significant departure from a baseline (null) model of the image. To infer image structure, we conduct a Bayesian analysis of a full model that uses a multiscale component to allow flexible departures from the posited null model. As a test statistic, we use a tail probability of the posterior distribution under the full model. This choice of test statistic allows us to estimate a computationally efficient upper bound on a p-value that enables us to draw strong conclusions even when there are limited computational resources that can be devoted to simulations under the null model. We demonstrate the statistical performance of our method on simulated images. Applying our method to an X-ray image of the quasar 0730+257, we find significant evidence against the null model of a single point source and uniform background, lending support to the claim of an X-ray jet

Enhanced Tetragonality in (\u3cem\u3ex\u3c/em\u3e)PbTiO\u3csub\u3e3\u3c/sub\u3e-(1-x)Bi(\u3cem\u3eB′B″\u3c/em\u3e)O\u3csub\u3e3\u3c/sub\u3e systems: Bi(Zn\u3csub\u3e3/4\u3c/sub\u3eWN\u3csub\u3e1/4\u3c/sub\u3e)O\u3csub\u3e3\u3c/sub\u3e

Solid solutions in the (x)PbTiO3–(1−x)Bi(Zn3/4W1/4)O3 system have been examined by x-ray diffraction, dielectric measurements, and thermal analysis. Bi(Zn3/4W1/4)O3increases the tetragonality and Curie temperature of PbTiO3 which reach a value of 1.08 and 530 °C, respectively, at the limit of the single-phase perovskite forming region (x~0.8). The observation of a sustained increase in the tetragonality in this system is similar to the behavior of the (x)PbTiO3–(1−x)Bi(Zn1/2Ti1/2)O3 system and highlights the unique properties of Bi-based systems when the B sites contain high concentrations of highly polarizable cations

Polarization and Charge Transfer in the Hydration of Chloride Ions

A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular dynamics simulations of a single chloride ion in bulk water. The simulations utilize the polarizable AMOEBA force field for trajectory generation, and MP2-level calculations are performed to examine the electronic structure properties of the ions and surrounding waters in the external field of more distant waters. The ChelpG method is employed to explore the effective charges and dipoles on the chloride ions and first-shell waters. The Quantum Theory of Atoms in Molecules (QTAIM) is further utilized to examine charge transfer from the anion to surrounding water molecules. From the QTAIM analysis, 0.2 elementary charges are transferred from the ion to the first-shell water molecules. The default AMOEBA model overestimates the average dipole moment magnitude of the ion compared with the estimated quantum mechanical value. The average magnitude of the dipole moment of the water molecules in the first shell treated at the MP2 level, with the more distant waters handled with an AMOEBA effective charge model, is 2.67 D. This value is close to the AMOEBA result for first-shell waters (2.72 D) and is slightly reduced from the bulk AMOEBA value (2.78 D). The magnitude of the dipole moment of the water molecules in the first solvation shell is most strongly affected by the local water-water interactions and hydrogen bonds with the second solvation shell, rather than by interactions with the ion.Comment: Slight revision, in press at J. Chem. Phy

Database management and analysis of fisheries in Illinois: Final report, 1 March 1999-28 February 2002

Issued May 2002; F-69-RReport issued on: May 200

Examining \u3cem\u3eDSM\u3c/em\u3e Criteria for Trichotillomania in A Dimensional Framework: Implications for \u3cem\u3eDSM-5\u3c/em\u3e And Diagnostic Practice

Background: Diagnosis of Trichotillomania (TTM) requires meeting several criteria that aim to embody the core pathology of the disorder. These criteria are traditionally interpreted monothetically, in that they are all equally necessary for diagnosis. Alternatively, a dimensional conceptualization of psychopathology allows for examination of the relatedness of each criterion to the TTM latent continuum. Objectives: First, to examine the ability of recently removed criteria (B and C) to identify the latent dimensions of TTM psychopathology, such that they discriminate between individuals with low and high degrees of hair pulling severity. Second, to determine the impact of removing criteria B and C on the information content of remaining diagnostic criteria. Third, to determine the psychometric properties of remaining TTM diagnostic criteria that remain largely unchanged in DSM-5; that is, whether they measure distinct or overlapping levels of TTM psychopathology. Fourth, to determine whether information content derived from diagnostic criteria aid in the prediction of disease trajectory (i.e., can relapse propensity be predicted from criteria endorsement patterns). Method: Statistics derived from Item Response Theory were used to examine diagnostic criteria endorsement in 91 adults with TTM who underwent psychotherapy. Results: The removal of two criteria in DSM-5 and psychometric validity of remaining criteria was supported. Additionally, individual trait parameters were used to predict treatment progress, uncovering predictive power where none previously existed. Conclusions: Diagnostic criteria for TTM should be examined in dimensional models, which allow for nuanced and sensitive measurement of core symptomology in treatment contexts