Réactivité de surface d'oxydes lamellaires, matériaux d'électrode positive dans des accumulateurs au lithium approches expérimentale et théorique

L'objectif de ce travail est de contribuer, par le biais d'approches expérimentales (XPS/chimisorption de sondes gazeuses) et théoriques (approches type DFT), à une meilleure compréhension fondamentale de la réactivité de surface de matériaux d'électrode positive et plus spécifiquement d'oxydes lamellaires lithiés LiMO2. La réactivité de surface du matériau LiCoO2 et l influence d une substitution de l atome de cobalt par l atome d aluminium a été étudiée pour avancer dans la compréhension de l effet bénéfique des coatings à base d alumine. L étude expérimentale a été centrée sur l adsorption de SO2 et montre que la présence d atomes d aluminium induit une diminution de réactivité : elle génère des espèces de type sulfite, différentes des sulfates seuls identifiés pour LiCoO2. La modélisation de cette adsorption permet la mise en évidence de deux modes d adsorption distincts : passage d un contrôle rédox pour LiCoO2 à un contrôle acido-basique pour des matériaux contenant des atomes d aluminium (LiAlO2), thermodynamiquement moins favorable. L influence de la nature du métal de transition a été analysée sur la base d études théoriques également menées sur LiMnO2 et LiNiO2. La modélisation de l adsorption de SO2 sur les surfaces des matériaux LiMO2 révèle la présence des deux processus de chimisorption (formation de sulfites et sulfates), avec mise en évidence du rôle important des cations de sous-surface dans les processus de réduction conduisant aux sulfates. Cette étude théorique a permis d interpréter les résultats expérimentaux obtenus pour Li(Ni1/3Mn1/3Co1/3)O2, l identification de sulfites résulterait de la présence des ions Ni2+ alors que celle de sulfates serait liée à la présence des ions Mn4+ et Co3+.This work is devoted to a better fundamental understanding of the surface reactivity of positive electrode materials, and specifically lamellar lithiated oxides LiMO2 through experimental (XPS/chemisorption of gaseous probes) and theoretical (DFT calculations) approaches. The beneficial effect of aluminum-based coatings on electrochemical performances is well known but the exact mechanisms are not totally understood. A detailed study of the surface reactivity of LiCoO2 and of the influence of Al/Co substitution is carried out. The experimental approach is focused on SO2 adsorption and shows that Al/Co substitution induces a decrease of the surface reactivity and a change in the nature of adsorbed species (identification of sulfite species whereas only sulfate species are characterized for LiCoO2). Theoretical calculations highlighs two different adsorption modes controlled by redox properties for LiCoO2 and by acid-base properties for -LiAlO2 (less energetically favorable). The theoretical study is extended to LiMnO2 and LiNiO2 in order to analyse the influence of the nature of the transition metal atom. The modelization of SO2 adsorption reveals two chemisorption processes (sulfite and sulfate formation), and highligths the key role of subsurface cations in the reduction process which leads to sulfates. Thus theoretical approach allows on interpretation of the experimental data obtained for Li(Ni1/3Mn1/3Co1/3)O2. The identification of sulfites may be explained by the presence of Ni2+ ions whereas sulfate species may result from the presence Mn4+ and Co3+ ions.PAU-BU Sciences (644452103) / SudocSudocFranceF

The large-scale Quasar-Lyman \alpha\ Forest Cross-Correlation from BOSS

We measure the large-scale cross-correlation of quasars with the Lyman \alpha\ forest absorption in redshift space, using ~ 60000 quasar spectra from Data Release 9 (DR9) of the Baryon Oscillation Spectroscopic Survey (BOSS). The cross-correlation is detected over a wide range of scales, up to comoving separations r of 80 Mpc/h. For r > 15 Mpc/h, we show that the cross-correlation is well fitted by the linear theory prediction for the mean overdensity around a quasar host halo in the standard \Lambda CDM model, with the redshift distortions indicative of gravitational evolution detected at high confidence. Using previous determinations of the Lyman \alpha\ forest bias factor obtained from the Lyman \alpha\ autocorrelation, we infer the quasar bias factor to be b_q = 3.64^+0.13_-0.15 at a mean redshift z=2.38, in agreement with previous measurements from the quasar auto-correlation. We also obtain a new estimate of the Lyman \alpha\ forest redshift distortion factor, \beta_F = 1.1 +/- 0.15, slightly larger than but consistent with the previous measurement from the Lyman \alpha\ forest autocorrelation. The simple linear model we use fails at separations r < 15 Mpc/h, and we show that this may reasonably be due to the enhanced ionization due to radiation from the quasars. We also provide the expected correction that the mass overdensity around the quasar implies for measurements of the ionizing radiation background from the line-of-sight proximity effect.Comment: 24 pages, 6 figures, published in JCA

Detection of Ly\beta auto-correlations and Ly\alpha-Ly\beta cross-correlations in BOSS Data Release 9

The Lyman-$\beta$ forest refers to a region in the spectra of distant quasars that lies between the rest-frame Lyman-$\beta$ and Lyman-$\gamma$ emissions. The forest in this region is dominated by a combination of absorption due to resonant Ly$\alpha$ and Ly$\beta$ scattering. When considering the 1D Ly$\beta$ forest in addition to the 1D Ly$\alpha$ forest, the full statistical description of the data requires four 1D power spectra: Ly$\alpha$ and Ly$\beta$ auto-power spectra and the Ly$\alpha$-Ly$\beta$ real and imaginary cross-power spectra. We describe how these can be measured using an optimal quadratic estimator that naturally disentangles Ly$\alpha$ and Ly$\beta$ contributions. Using a sample of approximately 60,000 quasar sight-lines from the BOSS Data Release 9, we make the measurement of the one-dimensional power spectrum of fluctuations due to the Ly$\beta$ resonant scattering. While we have not corrected our measurements for resolution damping of the power and other systematic effects carefully enough to use them for cosmological constraints, we can robustly conclude the following: i) Ly$\beta$ power spectrum and Ly$\alpha$-Ly$\beta$ cross spectra are detected with high statistical significance; ii) the cross-correlation coefficient is $\approx 1$ on large scales; iii) the Ly$\beta$ measurements are contaminated by the associated OVI absorption, which is analogous to the SiIII contamination of the Ly$\alpha$ forest. Measurements of the Ly$\beta$ forest will allow extension of the usable path-length for the Ly$\alpha$ measurements while allowing a better understanding of the physics of intergalactic medium and thus more robust cosmological constraints.Comment: 26 pages, 10 figures; matches version accepted by JCA

Baryon Acoustic Oscillations in the Ly{\alpha} forest of BOSS DR11 quasars

We report a detection of the baryon acoustic oscillation (BAO) feature in the flux-correlation function of the Ly{\alpha} forest of high-redshift quasars with a statistical significance of five standard deviations. The study uses 137,562 quasars in the redshift range $2.1\le z \le 3.5$ from the Data Release 11 (DR11) of the Baryon Oscillation Spectroscopic Survey (BOSS) of SDSS-III. This sample contains three times the number of quasars used in previous studies. The measured position of the BAO peak determines the angular distance, $D_A(z=2.34)$ and expansion rate, $H(z=2.34)$, both on a scale set by the sound horizon at the drag epoch, $r_d$. We find $D_A/r_d=11.28\pm0.65(1\sigma)^{+2.8}_{-1.2}(2\sigma)$ and $D_H/r_d=9.18\pm0.28(1\sigma)\pm0.6(2\sigma)$ where $D_H=c/H$. The optimal combination, $\sim D_H^{0.7}D_A^{0.3}/r_d$ is determined with a precision of $\sim2\%$. For the value $r_d=147.4~{\rm Mpc}$, consistent with the CMB power spectrum measured by Planck, we find $D_A(z=2.34)=1662\pm96(1\sigma)~{\rm Mpc}$ and $H(z=2.34)=222\pm7(1\sigma)~{\rm km\,s^{-1}Mpc^{-1}}$. Tests with mock catalogs and variations of our analysis procedure have revealed no systematic uncertainties comparable to our statistical errors. Our results agree with the previously reported BAO measurement at the same redshift using the quasar-Ly{\alpha} forest cross-correlation. The auto-correlation and cross-correlation approaches are complementary because of the quite different impact of redshift-space distortion on the two measurements. The combined constraints from the two correlation functions imply values of $D_A/r_d$ and $D_H/r_d$ that are, respectively, 7% low and 7% high compared to the predictions of a flat $\Lambda$CDM cosmological model with the best-fit Planck parameters. With our estimated statistical errors, the significance of this discrepancy is $\approx 2.5\sigma$.Comment: Accepted for publication in A&A. 17 pages, 18 figure

Deep Learning of Dark Energy Spectroscopic Instrument Mock Spectra to Find Damped Ly alpha Systems

We have updated and applied a convolutional neural network (CNN) machine-learning model to discover and characterize damped Lyα systems (DLAs) based on Dark Energy Spectroscopic Instrument (DESI) mock spectra. We have optimized the training process and constructed a CNN model that yields a DLA classification accuracy above 99% for spectra that have signal-to-noise ratios (S/N) above 5 per pixel. The classification accuracy is the rate of correct classifications. This accuracy remains above 97% for lower S/N ≈1 spectra. This CNN model provides estimations for redshift and H i column density with standard deviations of 0.002 and 0.17 dex for spectra with S/N above 3 pixel-1. Also, this DLA finder is able to identify overlapping DLAs and sub-DLAs. Further, the impact of different DLA catalogs on the measurement of baryon acoustic oscillations (BAO) is investigated. The cosmological fitting parameter result for BAO has less than 0.61% difference compared to analysis of the mock results with perfect knowledge of DLAs. This difference is lower than the statistical error for the first year estimated from the mock spectra: above 1.7%. We also compared the performances of the CNN and Gaussian Process (GP) models. Our improved CNN model has moderately 14% higher purity and 7% higher completeness than an older version of the GP code, for S/N > 3. Both codes provide good DLA redshift estimates, but the GP produces a better column density estimate by 24% less standard deviation. A credible DLA catalog for the DESI main survey can be provided by combining these two algorithms

Intrinsic Alignment as an RSD Contaminant in the DESI Survey

We measure the tidal alignment of the major axes of Luminous Red Galaxies (LRGs) from the Legacy Imaging Survey and use it to infer the artificial redshift-space distortion signature that will arise from an orientation-dependent, surface-brightness selection in the Dark Energy Spectroscopic Instrument (DESI) survey. Using photometric redshifts to down-weight the shape-density correlations due to weak lensing, we measure the intrinsic tidal alignment of LRGs. Separately, we estimate the net polarization of LRG orientations from DESI's fiber-magnitude target selection to be of order 10^-2 along the line of sight. Using these measurements and a linear tidal model, we forecast a 0.2% fractional decrease on the quadrupole of the 2-point correlation function for projected separations of 40-80 Mpc/h. We also use a halo catalog from the Abacus Summit cosmological simulation suite to reproduce this false quadrupole.Comment: 13 pages, 13 figures. Submitted to MNRAS. For an accessible summary of this paper, see https://cmlamman.github.io/doc/fakeRSD_summary.pd

Mock Quasar-Lyman-{\alpha} Forest Data-sets for the SDSS-III Baryon Oscillation Spectroscopic Survey

We describe mock data-sets generated to simulate the high-redshift quasar sample in Data Release 11 (DR11) of the SDSS-III Baryon Oscillation Spectroscopic Survey (BOSS). The mock spectra contain Ly{\alpha} forest correlations useful for studying the 3D correlation function including Baryon Acoustic Oscillations (BAO). They also include astrophysical effects such as quasar continuum diversity and high-density absorbers, instrumental effects such as noise and spectral resolution, as well as imperfections introduced by the SDSS pipeline treatment of the raw data. The Ly{\alpha} forest BAO analysis of the BOSS collaboration, described in Delubac et al. 2014, has used these mock data-sets to develop and cross-check analysis procedures prior to performing the BAO analysis on real data, and for continued systematic cross checks. Tests presented here show that the simulations reproduce sufficiently well important characteristics of real spectra. These mock data-sets will be made available together with the data at the time of the Data Release 11.Comment: 35 pages, 19 figures, Accepted by JCA

Chromosome-level genome assembly of Lilford's wall lizard, Podarcis lilfordi (Günther, 1874) from the Balearic Islands (Spain)

The Mediterranean lizard Podarcis lilfordi is an emblematic species of the Balearic Islands. The extensive phenotypic diversity among extant isolated populations makes the species a great insular model system for eco-evolutionary studies, as well as a challenging target for conservation management plans. Here we report the first high-quality chromosome-level assembly and annotation of the P. lilfordi genome, along with its mitogenome, based on a mixed sequencing strategy (10X Genomics linked reads, Oxford Nanopore Technologies long reads and Hi-C scaffolding) coupled with extensive transcriptomic data (Illumina and PacBio). The genome assembly (1.5 Gb) is highly contiguous (N50 = 90 Mb) and complete, with 99% of the sequence assigned to candidate chromosomal sequences and >97% gene completeness. We annotated a total of 25,663 protein-coding genes translating into 38,615 proteins. Comparison to the genome of the related species Podarcis muralis revealed substantial similarity in genome size, annotation metrics, repeat content, and a strong collinearity, despite their evolutionary distance (~18-20 MYA). This genome expands the repertoire of available reptilian genomes and will facilitate the exploration of the molecular and evolutionary processes underlying the extraordinary phenotypic diversity of this insular species, while providing a critical resource for conservation genomics.This study was supported by the Institut d’Estudis Catalans under the Catalan Initiative for the Earth Biogenome Project (PRO2020-S02 to L.B.), the Swedish Research Council (VR 2017-03846 and VR-2021-04656 to T.U. and VR-2020-03650 to N.F.) and Starting Grant from the European Research Council (no. 948126 to N.F.). We also acknowledge the support of the Spanish Ministry of Science and Innovation to the EMBL partnership, the Centro de Excelencia Severo Ochoa, the CERCA Programme/Generalitat de Catalunya, the Spanish Ministry of Science and Innovation through the Instituto de Salud Carlos III and the Generalitat de Catalunya through Departament de Salut and Departament d’Empresa i Coneixement. Co-financing funds were obtained from the European Regional Development Fund by the Spanish Ministry of Science and Innovation corresponding to the Programa Operativo FEDER Plurirregional de España (POPE) 2014-2020 and by the Secretaria d’Universitats i Recerca, Departament d’Empresa i Coneixement of the Generalitat de Catalunya corresponding to the Programa Operatiu FEDER de Catalunya 2014-2020.Peer reviewe

Inflation and Dark Energy from spectroscopy at z > 2

The expansion of the Universe is understood to have accelerated during two epochs: in its very first moments during a period of Inflation and much more recently, at z < 1, when Dark Energy is hypothesized to drive cosmic acceleration. The undiscovered mechanisms behind these two epochs represent some of the most important open problems in fundamental physics. The large cosmological volume at 2 < z < 5, together with the ability to efficiently target high-$z$ galaxies with known techniques, enables large gains in the study of Inflation and Dark Energy. A future spectroscopic survey can test the Gaussianity of the initial conditions up to a factor of ~50 better than our current bounds, crossing the crucial theoretical threshold of $\sigma(f_{NL}^{\rm local})$ of order unity that separates single field and multi-field models. Simultaneously, it can measure the fraction of Dark Energy at the percent level up to $z = 5$, thus serving as an unprecedented test of the standard model and opening up a tremendous discovery space

The Eighth Data Release of the Sloan Digital Sky Survey: First Data from SDSS-III

The Sloan Digital Sky Survey (SDSS) started a new phase in August 2008, with new instrumentation and new surveys focused on Galactic structure and chemical evolution, measurements of the baryon oscillation feature in the clustering of galaxies and the quasar Ly alpha forest, and a radial velocity search for planets around ~8000 stars. This paper describes the first data release of SDSS-III (and the eighth counting from the beginning of the SDSS). The release includes five-band imaging of roughly 5200 deg^2 in the Southern Galactic Cap, bringing the total footprint of the SDSS imaging to 14,555 deg^2, or over a third of the Celestial Sphere. All the imaging data have been reprocessed with an improved sky-subtraction algorithm and a final, self-consistent photometric recalibration and flat-field determination. This release also includes all data from the second phase of the Sloan Extension for Galactic Understanding and Evolution (SEGUE-2), consisting of spectroscopy of approximately 118,000 stars at both high and low Galactic latitudes. All the more than half a million stellar spectra obtained with the SDSS spectrograph have been reprocessed through an improved stellar parameters pipeline, which has better determination of metallicity for high metallicity stars.Comment: Astrophysical Journal Supplements, in press (minor updates from submitted version