Evaporation kinetics of Mg2SiO4 crystals and melts from molecular dynamics simulations

Computer simulations based on the molecular dynamics (MD) technique were used to study the mechanisms and kinetics of free evaporation from crystalline and molten forsterite (i.e., Mg2SiO4) on an atomic level. The interatomic potential employed for these simulations reproduces the energetics of bonding in forsterite and in gas-phase MgO and SiO2 reasonably accurately. Results of the simulation include predicted evaporation rates, diffusion rates, and reaction mechanisms for Mg2SiO4(s or l) yields 2Mg(g) + 20(g) + SiO2(g)

Local Structure and Dynamics in Methylammonium, Formamidinium, and Cesium Tin(II) Mixed-Halide Perovskites from 119Sn Solid-State NMR.

Organic-inorganic tin(II) halide perovskites have emerged as promising alternatives to lead halide perovskites in optoelectronic applications. While they suffer from considerably poorer performance and stability in comparison to their lead analogues, their performance improvements have so far largely been driven by trial and error efforts due to a critical lack of methods to probe their atomic-level microstructure. Here, we identify the challenges and devise a 119Sn solid-state NMR protocol for the determination of the local structure of mixed-cation and mixed-halide tin(II) halide perovskites as well as their degradation products and related phases. We establish that the longitudinal relaxation of 119Sn can span 6 orders of magnitude in this class of compounds, which makes judicious choice of experimental NMR parameters essential for the reliable detection of various phases. We show that Cl/Br and I/Br mixed-halide perovskites form solid alloys in any ratio, while only limited mixing is possible for I/Cl compositions. We elucidate the degradation pathways of Cs-, MA-, and FA-based tin(II) halides and show that degradation leads to highly disordered, qualitatively similar products, regardless of the A-site cation and halide. We detect the presence of metallic tin among the degradation products, which we suggest could contribute to the previously reported high conductivities in tin(II) halide perovskites. 119Sn NMR chemical shifts are a sensitive probe of the halide coordination environment as well as of the A-site cation composition. Finally, we use variable-temperature multifield relaxation measurements to quantify ion dynamics in MASnBr3 and establish activation energies for motion and show that this motion leads to spontaneous halide homogenization at room temperature whenever two different pure-halide perovskites are put in physical contact

A global atmospheric electricity monitoring network for climate and geophysical research

The Global atmospheric Electric Circuit (GEC) is a fundamental coupling network of the climate system connecting electrically disturbed weather regions with fair weather regions across the planet. The GEC sustains the fair weather electric field (or potential gradient, PG) which is present globally and can be measured routinely at the surface using durable instrumentation such as modern electric field mills, which are now widely deployed internationally. In contrast to lightning or magnetic fields, fair weather PG cannot be measured remotely. Despite the existence of many PG datasets (both contemporary and historical), few attempts have been made to coordinate and integrate these fragmented surface measurements within a global framework. Such a synthesis is important elvinin order to fully study major influences on the GEC such as climate variations and space weather effects, as well as more local atmospheric electrical processes such as cloud electrification, lightning initiation, and dust and aerosol charging. The GloCAEM (Global Coordination of Atmospheric Electricity Measurements) project has brought together experts in atmospheric electricity to make the first steps towards an effective global network for atmospheric electricity monitoring, which will provide data in near real time. Data from all sites are available in identically-formatted files, at both one second and one minute temporal resolution, along with meteorological data (wherever available) for ease of interpretation of electrical measurements. This work describes the details of the GloCAEM database and presents what is likely to be the largest single analysis of PG data performed from multiple datasets at geographically distinct locations. Analysis of the diurnal variation in PG from all 17 GloCAEM sites demonstrates that the majority of sites show two daily maxima, characteristic of local influences on the PG, such as the sunrise effect. Data analysis methods to minimise such effects are presented and recommendations provided on the most suitable GloCAEM sites for the study of various scientific phenomena. The use of the dataset for a further understanding of the GEC is also demonstrated, in particular for more detailed characterization of day-to-day global circuit variability. Such coordinated effort enables deeper insight into PG phenomenology which goes beyond single-location PG measurements, providing a simple measurement of global thunderstorm variability on a day-to-day timescale. The creation of the GloCAEM database is likely to enable much more effective study of atmospheric electricity variables than has ever been possible before, which will improve our understanding of the role of atmospheric electricity in the complex processes underlying weather and climate

Enhanced visible light absorption in layered Cs3Bi2Br9 through mixed-valence Sn(ii)/Sn(iv) doping

Funder: Cambridge TrustMixed valence Sn doping of Cs3Bi2Br9 leads to broad visible light absorption.</jats:p

Halide Mixing and Phase Segregation in Cs2AgBiX6 (X=Cl, Br, I) Double Perovskites from Cesium-133 Solid-State NMR and Optical Spectroscopy

All-inorganic double perovskites (elpasolites) are a promising potential alternative to lead halide perovskite in optoelectronic applications. While halide mixing is a well-established strategy for band gap tuning, little is known about halide mixing and phase segregation phenomena in double perovskites. Here, we synthesize a wide range of single− and mixed−halide Cs2AgBiX6 (X=Cl, Br, I) double perovskites using mechanosynthesis and probe their atomic-level microstructure using 133Cs solid-state MAS NMR. We show that mixed Cl/Br materials form pure phases for any Cl/Br ratio while Cl/I and Br/I mixing is only possible with-in a narrow range of halide ratios (<3 mol% I) and leads to a complex mixture of products for higher ratios. We characterize the optical properties of the resulting materials and show that halide mixing does not lead to an appreciable tunability of the PL emission. We find that iodide incorporation is particularly pernicious in that it quenches the PL emission intensity and radiative charge carrier lifetimes for iodide ratios as low as 0.3 mol%. Our study shows that sol-id-state NMR, in conjunction with optical spectroscopies, provides a comprehensive understanding of the structure-activity relationships, halide mixing and phase segregation phenomena in Cs2AgBiX6 (X=Cl, Br, I) double perovskites