226 research outputs found
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
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
Elucidation of the pre-nucleation phase directing metal-organic framework formation
Metal-organic framework (MOF) crystallization is governed by molecular assembly processes in the pre-nucleation stage. Yet, unravelling these pre-nucleation pathways and rationalizing their impact on crystal formation poses a great challenge since probing molecular-scale assemblies and macroscopic particles simultaneously is very complex. Herein, we present a multimodal, integrated approach to monitor MOF nucleation across multiple length scales by combining in situ optical spectroscopy, mass spectrometry, and molecular simulations. This approach allows tracing initial metal-organic complexes in solution and their assembly into oligomeric nuclei and simultaneously probing particle formation. During Co-ZIF-67 nucleation, a metal-organic pool forms with a variety of complexes caused by ligand exchange and symmetry reduction reactions. We discriminate complexes capable of initiating nucleation from growth species required for oligomerization into frameworks. Co4-nuclei are observed, which grow into particles following autocatalytic kinetics. The geometric and compositional variability of metal-organic pool species clarifies long-debated amorphous zeolitic imidazolate framework (ZIF)-particle nucleation and non-classic pathways of MOF crystallization
How may beach nourishment affect the sandy beach ecosystem? The case of Belgian beaches
Though often regarded as biological deserts, sandy beaches provide a unique habitat for several species. Research was conducted by a consortium of experts with as a first objective to provide an integrated overview of the Belgian beach ecosystem and all its major components. A second objective comprised a review of available literature on the ecological impact of beach nourishment. To meet the first objective, an integrated overview of the Belgian sandy beach ecosystem based on spatial and temporal variation of fauna and flora of 11 sandy beaches is provided. The presented results corroborate the overlooked ecological significance of sandy beaches as a habitat. Besides sedimentology and hydrodynamics, five ecosystem components were taken into account: microphytobenthos, vascular plants, terrestrial arthropods, zoobenthos and avifauna. Nourishment of beaches is a large scale anthropogenic influence on sandy beach ecosystem. Sandy beaches are regarded as systems with a strong resilience towards such impacts. Nevertheless serious (short term) ecological effects can be expected. A review of prior studies indicates that the impact of nourishment is rather case-specific and that it is difficult to draw general conclusions. Short term impact is mostly large due to total mortality of benthic life. It seems very likely that potential recovery from the impact of nourishment will be limited to two essential, species specific pathways: (1) survival by resident organisms and (2) re-colonisation by immigrating individuals, the latter depending on both the dispersal capacities and habitat demands of the organisms. Further research is needed to explore possibilities for reducing detrimental ecological effects. Specific studies are needed towards the survival options, the dispersal capacities and habitat demands of the species present. These should allow for management guidelines to be drawn in terms of preferable nourishment sediment characteristics, timing and practice of the deposition of the sand
- …