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Michelsen Engberg posted an update 8 hours, 52 minutes ago
We report on a Python toolbox for unbiased statistical analysis of fluorescence intermittency properties of single emitters. Intermittency, that is, step-wise temporal variations in the instantaneous emission intensity and fluorescence decay rate properties, is common to organic fluorophores, II-VI quantum dots, and perovskite quantum dots alike. Unbiased statistical analysis of intermittency switching time distributions, involved levels, and lifetimes are important to avoid interpretation artifacts. This work provides an implementation of Bayesian changepoint analysis and level clustering applicable to time-tagged single-photon detection data of single emitters that can be applied to real experimental data and as a tool to verify the ramifications of hypothesized mechanistic intermittency models. We provide a detailed Monte Carlo analysis to illustrate these statistics tools and to benchmark the extent to which conclusions can be drawn on the photophysics of highly complex systems, such as perovskite quantum dots that switch between a plethora of states instead of just two.Two-dimensional (2D) transition-metal monochalcogenides have been recently predicted to be potential photo(electro)catalysts for water splitting and photoelectrochemical (PEC) reactions. Differently from the most established InSe, GaSe, GeSe, and many other monochalcogenides, bulk GaS has a large band gap of ∼2.5 eV, which increases up to more than 3.0 eV with decreasing its thickness due to quantum confinement effects. Therefore, 2D GaS fills the void between 2D small-band-gap semiconductors and insulators, resulting of interest for the realization of van der Waals type-I heterojunctions in photocatalysis, as well as the development of UV light-emitting diodes, quantum wells, and other optoelectronic devices. Based on theoretical calculations of the electronic structure of GaS as a function of layer number reported in the literature, we experimentally demonstrate, for the first time, the PEC properties of liquid-phase exfoliated GaS nanoflakes. Our results indicate that solution-processed 2D GaS-based PEC-typplications.The photoexcited triplet states of porphyrin architectures are of significant interest in a wide range of fields including molecular wires, nonlinear optics, and molecular spintronics. Electron paramagnetic resonance (EPR) is a key spectroscopic tool in the characterization of these transient paramagnetic states singularly well suited to quantify spin delocalization. Previous work proposed a means of extracting the absolute signs of the zero-field splitting (ZFS) parameters, D and E, and triplet sublevel populations by transient continuous wave, hyperfine measurements, and magnetophotoselection. Here, we present challenges of this methodology for a series of meso-perfluoroalkyl-substituted zinc porphyrin monomers with orthorhombic symmetries, where interpretation of experimental data must proceed with caution and the validity of the assumptions used in the analysis must be scrutinized. The EPR data are discussed alongside quantum chemical calculations, employing both DFT and CASSCF methodologies. Despite some success of the latter in quantifying the magnitude of the ZFS interaction, the results clearly provide motivation to develop improved methods for ZFS calculations of highly delocalized organic triplet states.We report nitric oxide (NO) desorption rates from Pd(111) and Pd(332) surfaces measured with velocity-resolved kinetics. The desorption rates at the surface temperatures from 620 to 800 K span more than 3 orders of magnitude, and competing processes, like dissociation, are absent. Applying transition state theory (TST) to model experimental data leads to the NO binding energy E 0 = 1.766 ± 0.024 eV and diffusion barrier D T = 0.29 ± 0.11 eV on the (111) terrace and the stabilization energy for (110)-steps ΔE ST = 0.060-0.030 +0.015 eV. These parameters provide valuable benchmarks for theory.We study ionic liquid-solvent mixtures in slit-shaped nanopores wider than a few ion diameters. Using a continuum theory and generic thermodynamic reasoning, we reveal that such systems can undergo a capillary ionization transition. At this transition, the pores spontaneously ionize or deionize upon infinitesimal changes of temperature, slit width, or voltage. Our calculations show that a voltage applied to a pore may induce a capillary ionization, which-counterintuitively-is followed by a re-entrant deionization as the voltage increases. We find that such ionization transitions produce sharp jumps in the accumulated charge and stored energy, which may find useful applications in energy storage and heat-to-energy conversion.Porosity in functional oxide nanorods is a recently discovered new type of microstructure, which is not yet fully understood and still under evaluation for its impact on applications in catalysis and gas/ion storage. Here we explore the shape and distribution of pores in ceria in three dimensions using a modified algorithm of geometric tomography as a reliable tool for reconstructing defective and strained nanoobjects. The pores are confirmed as “negative-particle” or “inverse-particle” cuboctahedral shapes located exclusively beneath the flat surface of the rods separated via a sub-5 nm thin ceria wall from the outside. New findings also comprise elongated “negative-rod” defects, seen as embryonic nanotubes, and pores in cube-shaped ceria. Furthermore, we report near-sintering secondary heat treatment of nanorods and cubes, confirming persistence of pores beyond external surface rounding. We support our experiments with molecular modeling and predict that the growth history of voids is via diffusion and aggregation of atomic point defects. In addition, we use density functional theory to show that the relative stability of pore (shape) increases in the order “cuboidal” less then “hexagonal-prismatic” less then “octahedral”. selleck compound The results indicate that by engineering voids into nanorods, via a high-temperature postsynthetic heat treatment, a potential future alternative route of tuning catalytic activities might become possible.