RESUMO
The structure of amorphous silicon (a-Si) is widely thought of as a fourfold-connected random network, and yet it is defective atoms, with fewer or more than four bonds, that make it particularly interesting. Despite many attempts to explain such "dangling-bond" and "floating-bond" defects, respectively, a unified understanding is still missing. Here, we use advanced computational chemistry methods to reveal the complex structural and energetic landscape of defects in a-Si. We study an ultra-large-scale, quantum-accurate structural model containing a million atoms, and thousands of individual defects, allowing reliable defect-related statistics to be obtained. We combine structural descriptors and machine-learned atomic energies to develop a classification of the different types of defects in a-Si. The results suggest a revision of the established floating-bond model by showing that fivefold-bonded atoms in a-Si exhibit a wide range of local environments-analogous to fivefold centers in coordination chemistry. Furthermore, it is shown that fivefold (but not threefold) coordination defects tend to cluster together. Our study provides new insights into one of the most widely studied amorphous solids, and has general implications for understanding defects in disordered materials beyond silicon alone.
RESUMO
Harmattan dust and traffic-related pollution have been a serious environmental concern in the West African sub-region. In order to further contribute to the understanding of ambient levels of atmospheric pollution and chemical composition in the region, this study monitored harmattan dust and traffic-related particulate matter at four locations across southwestern (Ile-Ife) and north-western (Zaria) geo-political zones of Nigeria. The collected samples were characterized for their chemical composition using Energy-Dispersive X-Ray Fluorescence spectrometer equipped with an optimized secondary target x-ray excitation conditions (Al, CaF2, Fe, Ge, Zr, Mo, Ag, Al2O3). The objectives are to assess spatio-temporal mass concentrations, chemical footprints, enrichment factors, elemental correlations, and ratios at all locations. The X-ray analytical method was validated with a NIST SRM 2783 air particulate standard, and detection limits for each chemical specie were determined. Validation results showed good reproducibility of the certified reference material with relative standard deviations of the elements much lower by about 1-13% than the corresponding reference values. Mass concentrations reached up to 2200 µgm-3 in the north and 1500 µgm-3 in the south. The range of mean concentration of crustal marker elements were Al (5-27 µgm-3), Si (5-856 µgm-3), Ca (0.78-13 µgm-3), and Fe (2-13 µgm-3), and were most abundant during the harmattan particularly in the southwestern region. Highest mean concentration values of 380, 810, and 420 ngm-3 were recorded for Cr, Cu, and Pb respectively at the traffic corridor which also recorded the highest enrichment factors. Black carbon and elemental concentrations contributed between 1 to 54% and 9 to 94% across the locations respectively. Backward trajectories of atmospheric flow over the locations showed two dominant sources; dust laden source from the Sahara desert and maritime flow over the Gulf of Guinea. This study found that chemical footprints (Al, Si, K, Ca, Ti, and Fe) of harmattan-related dust were more correlated (r2 between 0.88 and 0.99) than those attributed to dust re-suspension at the traffic location.
