Surface Reconstruction and Lateral Adsorbate Interactions on Cobalt-Based Catalysts An Investigation Using Lattice Gas Models and Density Functional Theory

This dissertation deals with the problem of computationally determining the structure and catalytically active phase of cobalt-based Fischer-Tropsch (FT) catalysts driven toward oxygenates. Cobalt-copper based catalysts are examined first using density functional theory calculations. The interactions of carbon monoxide (CO) with cobalt-copper nanoparticle surfaces are analyzed for CO's possible role in restructuring these nanoparticles and subsequent creation of the catalytically active phase. It is shown that cobalt-copper catalysts preferentially form Co Cu core-shell nanoparticles, and that CO can induce up to half of step edge and one quarter of terrace copper atoms to be substituted with cobalt atoms from the core. Cobalt enrichment is limited due to the formation of cobalt subcarbonyl complexes. These complexes are shown to be capable of rupturing and diffusing across the surface, providing the ingredients needed for nanoisland formation and facet reconstruction. This work points to new models that are likely important to cobalt-copper catalyzed FT. New lattice gas (LG) cluster expansion (CE) tools are also developed in this dissertation via the development of the ab initio Mean-field Augmented Lattice Gas Modeling (AMALGM) code. A new theoretical reformulation of the CE formalism, which is more appropriate for the LG paradigm, is detailed. AMALGM is designed to use a newly developed convergent version of the leave-multiple-out cross-validation (LMO-CV) score as the objective function for optimization of LG CEs. A new method for quantifying the errors of the effective cluster interactions of CEs is also developed. This error quantification is shown to capture the uncertainty in CEs due to geometric relaxations in DFT data. AMALGM and these new methods are then utilized to investigate the differences in CO adsorption energetics on the face centered cubic (fcc) and hexagonal close packed (hcp) phases of cobalt relevant to FT. It is shown that the first nearest neighbor (1NN) dominates and is very repulsive in both but significantly more repulsive for fcc cobalt. At high chemical potentials, 1NN CO pairings may be allowed on hcp cobalt where they are still energetically prohibited on fcc cobalt, suggesting a potential source for the reduced activity observed on hcp cobalt catalysts

A Large, Uniform Sample of X-Ray-emitting AGNs: Selection Approach and an Initial Catalog from the ROSAT All-Sky and Sloan Digital Sky Surveys

Many open questions in X-ray astronomy are limited by the relatively small number of objects in uniform optically identified and observed samples, especially when rare subclasses are considered or when subsets are isolated to search for evolution or correlations between wavebands. We describe the initial results of a new program aimed to ultimately yield ~10⁴ fully characterized X-ray source identifications—a sample about an order of magnitude larger than earlier efforts. The technique is detailed and employs X-ray data from the ROSAT All-Sky Survey (RASS) and optical imaging and spectroscopic follow-up from the Sloan Digital Sky Survey (SDSS); these two surveys prove to be serendipitously very well matched in sensitivity. As part of the SDSS software pipelines, optical objects in the SDSS photometric catalogs are automatically positionally cross-correlated with RASS X-ray sources. Then priorities for follow-on SDSS optical spectra of candidate counterparts are automatically assigned using an algorithm based on the known ratios of f_x/f_opt for various classes of X-ray emitters at typical RASS fluxes of ~10⁻¹³ ergs cm⁻² s⁻¹. SDSS photometric parameters for optical morphology, magnitude, and colors, plus FIRST radio information, serve as proxies for object class. Initial application of this approach to RASS/SDSS data from 1400 deg² of sky provides a catalog of more than 1200 spectroscopically confirmed quasars and other AGNs that are probable RASS identifications. Most of these are new identifications, and only a few percent of the AGN counterparts are likely to be random superpositions. The magnitude and redshift ranges of the counterparts are very broad, extending over 15 < m < 21 and 0.03 < z < 3.6, respectively. Although most identifications are quasars and Seyfert 1 galaxies, a variety of other AGN subclasses are also sampled. Substantial numbers of rare AGN types are found, including more than 130 narrow-line Seyfert 1 galaxies and 45 BL Lac candidates. These early results already provide a very sizable set of source identifications, demonstrate the utility of the sample in multiwaveband investigations, and show the capability of the joint RASS/SDSS approach to efficiently proceed toward the largest homogeneously selected/observed sample of X-ray–emitting quasars and other kinds of AGNs

A Large, Uniform Sample of X-ray Emitting AGN from the ROSAT All-Sky and Sloan Digital Sky Surveys: the Data Release 5 Sample

We describe further results of a program aimed to yield ~10^4 fully characterized optical identifications of ROSAT X-ray sources. Our program employs X-ray data from the ROSAT All-Sky Survey (RASS), and both optical imaging and spectroscopic data from the Sloan Digital Sky Survey (SDSS). RASS/SDSS data from 5740 deg^2 of sky spectroscopically covered in SDSS Data Release 5 (DR5) provide an expanded catalog of 7000 confirmed quasars and other AGN that are probable RASS identifications. Again in our expanded catalog, the identifications as X-ray sources are statistically secure, with only a few percent of the SDSS AGN likely to be randomly superposed on unrelated RASS X-ray sources. Most identifications continue to be quasars and Seyfert 1s with 15<m<21 and 0.01<z<4; but the total sample size has grown to include very substantial numbers of even quite rare AGN, e.g., now including several hundreds of candidate X-ray emitting BL Lacs and narrow-line Seyfert 1 galaxies. In addition to exploring rare subpopulations, such a large total sample may be useful when considering correlations between the X-ray and the optical, and may also serve as a resource list from which to select the "best" object (e.g., X-ray brightest AGN of a certain subclass, at a preferred redshift or luminosity) for follow-on X-ray spectral or alternate detailed studies.Comment: Accepted for publication in AJ; 32 pages, including 11 figures, and 6 example table

An Initial Survey of White Dwarfs in the Sloan Digital Sky Survey

An initial assessment is made of white dwarf and hot subdwarf stars observed in the Sloan Digital Sky Survey. In a small area of sky (190 square degrees), observed much like the full survey will be, 269 white dwarfs and 56 hot subdwarfs are identified spectroscopically where only 44 white dwarfs and 5 hot subdwarfs were known previously. Most are ordinary DA (hydrogen atmosphere) and DB (helium) types. In addition, in the full survey to date, a number of WDs have been found with uncommon spectral types. Among these are blue DQ stars displaying lines of atomic carbon; red DQ stars showing molecular bands of C_2 with a wide variety of strengths; DZ stars where Ca and occasionally Mg, Na, and/or Fe lines are detected; and magnetic WDs with a wide range of magnetic field strengths in DA, DB, DQ, and (probably) DZ spectral types. Photometry alone allows identification of stars hotter than 12000 K, and the density of these stars for 15<g<20 is found to be ~2.2 deg^{-2} at Galactic latitudes 29-62 deg. Spectra are obtained for roughly half of these hot stars. The spectra show that, for 15<g<17, 40% of hot stars are WDs and the fraction of WDs rises to ~90% at g=20. The remainder are hot sdB and sdO stars.Comment: Accepted for AJ; 43 pages, including 12 figures and 5 table

A Large Sample of BL Lacs from SDSS and FIRST

We present a large sample of 501 radio-selected BL Lac candidates from the combination of the Sloan Digital Sky Survey (SDSS) Data Release 5 optical spectroscopy and from the Faint Images of the Radio Sky at Twenty-Centimeters (FIRST) radio survey; this is one of the largest BL Lac samples yet assembled, and each object emerges with homogeneous data coverage. Each candidate is detected in the radio from FIRST and confirmed in SDSS optical spectroscopy to have: (1) no emission feature with measured rest equivalent width larger than 5 Angstroms; and (2) no measured Ca II H/K depression larger than 40%. We subdivide our sample into 426 higher confidence candidates and 75 lower confidence candidates. We argue that contamination from other classes of objects that formally pass our selection criteria is small, and we identify a few very rare radio AGN with unusual spectra that are probably related to broad absorption line quasars. About one-fifth of our sample were known BL Lacs prior to the SDSS. A preliminary analysis of the sample generally supports the standard beaming paradigm. While we recover sizable numbers of low-energy and intermediate-energy cutoff BL Lacs (LBLs and IBLs, respectively), there are indications of a potential bias toward recovering high-energy cutoff BL Lacs (HBLs) from SDSS spectroscopy. Such a large sample may eventually provide new constraints on BL Lac unification models and their potentially peculiar cosmic evolution; in particular, our sample contains a significant number of higher redshift objects, a sub-population for which the standard paradigm has yet to be rigorously constrained.Comment: 16 pages, 13 figures, 6 tables. Accepted for Publication in the Astronomical Journa

A Large, Uniform Sample of X-ray Emitting AGN: Selection Approach and an Initial Catalog from the ROSAT All-Sky and Sloan Digital Sky Surveys

Many open questions in X-ray astronomy are limited by the relatively small number of objects in uniform optically-identified samples, especially when rare subclasses are considered, or subsets isolated to search for evolution or correlations between wavebands. We describe initial results of a program aimed to ultimately yield 10^4 X-ray source identifications--a sample about an order of magnitude larger than earlier efforts. The technique employs X-ray data from the ROSAT All-Sky Survey (RASS), and optical imaging and spectroscopic followup from the Sloan Digital Sky Survey (SDSS). Optical objects in the SDSS catalogs are automatically cross-correlated with RASS X-ray source positions; then priorities for follow-on SDSS optical spectra of candidate counterparts are automatically assigned using an algorithm based on the known fx/fopt ratios for various classes of X-ray emitters. SDSS parameters for optical morphology, magnitude, colors, plus FIRST radio data, serve as proxies for object class. Initial application of this approach to 1400 deg^2 of sky provides a catalog of 1200 spectroscopically confirmed quasars/AGN that are probable RASS identifications. Most of the IDs are new, and only a few percent of the AGN are likely to be random superpositions. The magnitude and redshift ranges of the counterparts extend over 15<m<21 and 0.03<z<3.6. Although most IDs are quasars and Sy 1s, a variety of other AGN subclasses are also sampled. Substantial numbers of rare AGN are found, including more than 130 narrow-line Seyfert 1s and 45 BL Lac candidates. These results already provide a sizeable set of new IDs, show utility of the sample in multi-waveband studies, and demonstrate the capability of the RASS/SDSS approach to efficiently proceed towards the largest homogeneously selected/observed sample of X-ray emitting AGN. Abridged AbstractComment: 39 pages, 11 bitmapped figs (PDF view or print OK). Version accepted by AJ: slightly expanded sample, 1 new fig, minor modification

Using the Fundamental Plane of Black Hole Activity to Distinguish X-ray Processes from Weakly Accreting Black Holes

The fundamental plane of black hole activity is a relation between X-ray luminosity, radio luminosity, and black hole mass for hard state Galactic black holes and their supermassive analogs. The fundamental plane suggests that, at low-accretion rates, the physical processes regulating the conversion of an accretion flow into radiative energy could be universal across the entire black hole mass scale. However, there is still a need to further refine the fundamental plane in order to better discern the radiative processes and their geometry very close to the black hole, in particular the source of hard X-rays. Further refinement is necessary because error bars on the best-fit slopes of the fundamental plane are generally large, and also the inferred coefficients can be sensitive to the adopted sample of black holes. In this work, we regress the fundamental plane with a Bayesian technique. Our approach shows that sub-Eddington black holes emit X-ray emission that is predominantly optically thin synchrotron radiation from the jet, provided that their radio spectra are flat or inverted. X-ray emission dominated by very radiatively inefficient accretion flows are excluded at the >3\sigma\ level. We also show that it is difficult to place FR I galaxies onto the fundamental plane because their X-ray jet emission is highly affected by synchrotron cooling. On the other hand, BL Lac objects fit onto the fundamental plane. Including a uniform subset of high-energy peaked BL Lac objects from the SDSS, we find sub-Eddington black holes with flat/inverted radio spectra follow log L_x=(1.45\pm0.04)log L_R-(0.88\pm0.06)\logM_{BH}-6.07\pm1.10, with \sigma_{int}=0.07\pm0.05 dex. Finally, we discuss how the effects of synchrotron cooling of jet emission from the highest black hole masses can bias fundamental plane regressions, perhaps leading to incorrect inferences on X-ray radiation mechanisms.Comment: 23 pages, 8 figures, 3 tables. Accepted for publication in MNRA

Distinct Type of Transmission Barrier Revealed by Study of Multiple Prion Determinants of Rnq1

Prions are self-propagating protein conformations. Transmission of the prion state between non-identical proteins, e.g. between homologous proteins from different species, is frequently inefficient. Transmission barriers are attributed to sequence differences in prion proteins, but their underlying mechanisms are not clear. Here we use a yeast Rnq1/[PIN+]-based experimental system to explore the nature of transmission barriers. [PIN+], the prion form of Rnq1, is common in wild and laboratory yeast strains, where it facilitates the appearance of other prions. Rnq1's prion domain carries four discrete QN-rich regions. We start by showing that Rnq1 encompasses multiple prion determinants that can independently drive amyloid formation in vitro and transmit the [PIN+] prion state in vivo. Subsequent analysis of [PIN+] transmission between Rnq1 fragments with different sets of prion determinants established that (i) one common QN-rich region is required and usually sufficient for the transmission; (ii) despite identical sequences of the common QNs, such transmissions are impeded by barriers of different strength. Existence of transmission barriers in the absence of amino acid mismatches in transmitting regions indicates that in complex prion domains multiple prion determinants act cooperatively to attain the final prion conformation, and reveals transmission barriers determined by this cooperative fold

The First Data Release of the Sloan Digital Sky Survey

The Sloan Digital Sky Survey has validated and made publicly available its First Data Release. This consists of 2099 square degrees of five-band (u, g, r, i, z) imaging data, 186,240 spectra of galaxies, quasars, stars and calibrating blank sky patches selected over 1360 square degrees of this area, and tables of measured parameters from these data. The imaging data go to a depth of r ~ 22.6 and are photometrically and astrometrically calibrated to 2% rms and 100 milli-arcsec rms per coordinate, respectively. The spectra cover the range 3800--9200 A, with a resolution of 1800--2100. Further characteristics of the data are described, as are the data products themselves.Comment: Submitted to The Astronomical Journal. 16 pages. For associated documentation, see http://www.sdss.org/dr

A novel Alzheimer disease locus located near the gene encoding tau protein

This is the author accepted manuscript. The final version is available from the publisher via the DOI in this recordAPOE ε4, the most significant genetic risk factor for Alzheimer disease (AD), may mask effects of other loci. We re-analyzed genome-wide association study (GWAS) data from the International Genomics of Alzheimer's Project (IGAP) Consortium in APOE ε4+ (10 352 cases and 9207 controls) and APOE ε4- (7184 cases and 26 968 controls) subgroups as well as in the total sample testing for interaction between a single-nucleotide polymorphism (SNP) and APOE ε4 status. Suggestive associations (P<1 × 10-4) in stage 1 were evaluated in an independent sample (stage 2) containing 4203 subjects (APOE ε4+: 1250 cases and 536 controls; APOE ε4-: 718 cases and 1699 controls). Among APOE ε4- subjects, novel genome-wide significant (GWS) association was observed with 17 SNPs (all between KANSL1 and LRRC37A on chromosome 17 near MAPT) in a meta-analysis of the stage 1 and stage 2 data sets (best SNP, rs2732703, P=5·8 × 10-9). Conditional analysis revealed that rs2732703 accounted for association signals in the entire 100-kilobase region that includes MAPT. Except for previously identified AD loci showing stronger association in APOE ε4+ subjects (CR1 and CLU) or APOE ε4- subjects (MS4A6A/MS4A4A/MS4A6E), no other SNPs were significantly associated with AD in a specific APOE genotype subgroup. In addition, the finding in the stage 1 sample that AD risk is significantly influenced by the interaction of APOE with rs1595014 in TMEM106B (P=1·6 × 10-7) is noteworthy, because TMEM106B variants have previously been associated with risk of frontotemporal dementia. Expression quantitative trait locus analysis revealed that rs113986870, one of the GWS SNPs near rs2732703, is significantly associated with four KANSL1 probes that target transcription of the first translated exon and an untranslated exon in hippocampus (P≤1.3 × 10-8), frontal cortex (P≤1.3 × 10-9) and temporal cortex (P≤1.2 × 10-11). Rs113986870 is also strongly associated with a MAPT probe that targets transcription of alternatively spliced exon 3 in frontal cortex (P=9.2 × 10-6) and temporal cortex (P=2.6 × 10-6). Our APOE-stratified GWAS is the first to show GWS association for AD with SNPs in the chromosome 17q21.31 region. Replication of this finding in independent samples is needed to verify that SNPs in this region have significantly stronger effects on AD risk in persons lacking APOE ε4 compared with persons carrying this allele, and if this is found to hold, further examination of this region and studies aimed at deciphering the mechanism(s) are warranted