Computation of charge distribution and electrostatic potential in silicates with the use of chemical potential equalization models

New parameters for the electronegativity equalization model (EEM) and the split-charge equilibration (SQE) model are calibrated for silicate materials, based on an extensive training set of representative isolated systems. In total, four calibrations are carried out, two for each model, either using iterative Hirshfeld (HI) charges or ESP grid data computed with density functional theory (DFT) as a reference. Both the static (ground state) reference quantities and their responses to uniform electric fields are included in the fitting procedure. The EEM model fails to describe the response data, whereas the SQE model quantitatively reproduces all of the training data. For the ESP-based parameters, we found that the reference ESP data are only useful at those grid points where the electron density is lower than 0.001 a.u. The density value correlates with a distance criterion used for selecting grid points in common ESP fitting schemes. All parameters are validated with DFT computations on an independent set of isolated systems (similar to the training set), and on a set of periodic systems including dense and microporous crystalline silica structures, zirconia, and zirconium silicate. Although the transferability of the parameters to new isolated systems poses no difficulties, the atomic hardness parameters in the HI-based models must be corrected to obtain accurate results for periodic systems. The SQE/ESP model permits the calculation of the ESP with similar accuracy in both isolated and periodic systems

Images, structural properties and metal abundances of galaxy clusters observed with Chandra ACIS-I at 0.1<z<1.3

We have assembled a sample of 115 galaxy clusters at 0.1<z<1.3 with archived Chandra ACIS-I observations. We present X-ray images of the clusters and make available region files containing contours of the smoothed X-ray emission. The structural properties of the clusters were investigated and we found a significant absence of relaxed clusters (as determined by centroid shift measurements) at z>0.5. The slope of the surface brightness profiles at large radii were steeper on average by 15% than the slope obtained by fitting a simple beta-model to the emission. This slope was also found to be correlated with cluster temperature, with some indication that the correlation is weaker for the clusters at z>0.5. We measured the mean metal abundance of the cluster gas as a function of redshift and found significant evolution, with the abundances dropping by 50% between z=0.1 and z~1. This evolution was still present (although less significant) when the cluster cores were excluded from the abundance measurements, indicating that the evolution is not solely due to the disappearance of relaxed, cool core clusters (which are known to have enhanced core metal abundances) from the population at z>0.5.Comment: 23 pages, 12 figures. Accepted for publication in ApJS. Updated to match published version. Redshifts of two clusters (RXJ1701 and CL0848) corrected and two observations of MACSJ0744.8 have been combined into one. Conclusions unchanged. A version with images of all of the clusters is available at http://hea-www.harvard.edu/~bmaughan/clusters.htm

Error estimates for solid-state density-functional theory predictions: an overview by means of the ground-state elemental crystals

Predictions of observable properties by density-functional theory calculations (DFT) are used increasingly often in experimental condensed-matter physics and materials engineering as data. These predictions are used to analyze recent measurements, or to plan future experiments. Increasingly more experimental scientists in these fields therefore face the natural question: what is the expected error for such an ab initio prediction? Information and experience about this question is scattered over two decades of literature. The present review aims to summarize and quantify this implicit knowledge. This leads to a practical protocol that allows any scientist - experimental or theoretical - to determine justifiable error estimates for many basic property predictions, without having to perform additional DFT calculations. A central role is played by a large and diverse test set of crystalline solids, containing all ground-state elemental crystals (except most lanthanides). For several properties of each crystal, the difference between DFT results and experimental values is assessed. We discuss trends in these deviations and review explanations suggested in the literature. A prerequisite for such an error analysis is that different implementations of the same first-principles formalism provide the same predictions. Therefore, the reproducibility of predictions across several mainstream methods and codes is discussed too. A quality factor Delta expresses the spread in predictions from two distinct DFT implementations by a single number. To compare the PAW method to the highly accurate APW+lo approach, a code assessment of VASP and GPAW with respect to WIEN2k yields Delta values of 1.9 and 3.3 meV/atom, respectively. These differences are an order of magnitude smaller than the typical difference with experiment, and therefore predictions by APW+lo and PAW are for practical purposes identical.Comment: 27 pages, 20 figures, supplementary material available (v5 contains updated supplementary material

Determination of the nature of the Cu coordination complexes formed in the presence of NO and NH3 within SSZ-13

Ammonia-selective catalytic reduction (NH3-SCR) using Cu zeolites is a well-established strategy for the abatement of NOx gases. Recent studies have demonstrated that Cu is particularly active when exchanged into the SSZ-13 zeolite, and its location in either the 6r or 8r renders it an excellent model system for fundamental studies. In this work, we examine the interaction of NH3-SCR relevant gases (NO and NH3) with the Cu2+ centers within the SSZ-13 structure, coupling powder diffraction (PD), X-ray absorption spectroscopy (XAFS), and density functional theory (DFT). This combined approach revealed that, upon calcination, cooling and gas exposure Cu ions tend to locate in the 8r window. After NO introduction, Cu-ions are seen to coordinate to two framework oxygens and one NO molecule, resulting in a bent Cu-nitrosyl complex with a Cu-N-O bond angle of similar to 150 degrees. Whilst Cu seems to be partially reduced/changed in coordination state, NO is partially oxidized. On exposure to NH3 while the PD data suggest the Cu2+ ion occupies a similar position, simulation and XAFS pointed toward the formation of a Jahn-Teller distorted hexaamine complex [Cu(NH3)(6)](2+) in the center of the cha cage. These results have important implications in terms of uptake and storage of these reactive gases and potentially for the mechanisms involved in the NH3-SCR process

Chandra temperature profiles for a sample of nearby relaxed galaxy clusters

We present Chandra gas temperature profiles at large radii for a sample of 13 nearby, relaxed galaxy clusters and groups, which includes A133, A262, A383, A478, A907, A1413, A1795, A1991, A2029, A2390, MKW4, RXJ1159+5531, and USGC S152. The sample covers a range of average temperatures from 1 to 10 keV. The clusters are selected from the archive or observed by us to have sufficient exposures and off-center area coverage to enable accurate background subtraction and reach the temperature accuracy of better than 20-30% at least to r=0.4-0.5 r_180, and for the three best clusters, to 0.6-0.7 r_180. For all clusters, we find cool gas in the cores, outside of which the temperature reaches a peak at r =~ 0.15 r_180 and then declines to ~0.5 of its peak value at r =~ 0.5 r_180. When the profiles are scaled by the cluster average temperature (excluding cool cores) and the estimated virial radius, they show large scatter at small radii, but remarkable similarity at r>0.1-0.2 r_180 for all but one cluster (A2390). Our results are in good agreement with previous measurements from ASCA by Markevitch et al. and from Beppo-SAX by DeGrandi & Molendi. Four clusters have recent XMM-Newton temperature profiles, two of which agree with our results, and we discuss reasons for disagreement for the other two. The overall shape of temperature profiles at large radii is reproduced in recent cosmological simulations.Comment: ApJ in press. Replaced to synchronize with accepted version. Analysis for two clusters (A2029 and RXJ1159) adde