Recent progress in the consistent interpretation of complementary spectroscopic results obtained on molecular systems

Abstract Research on organic thin films is largely driven by potential (opto‐)electronic applications and turns out to be no less intriguing from a fundamental point of view. Numerous studies make it clear that the understanding of device‐relevant molecular thin film architectures is quite challenging—often hampered by insufficient spectroscopic data and the lack of a consistent interpretation of the available datasets. Consequently, speculative aspects prevail in the discussion of energy levels in conjunction with the optical properties of organic thin films. Adequate spectroscopic techniques applicable to thin films of organic molecules (typical thicknesses required for devices are in the nanometer range) with the necessary sensitivities are rather demanding. Some of those methods were developed or significantly improved in the recent past. Here, the now available complementary spectroscopies are briefly surveyed with particular emphasis on some techniques that have not yet become widespread standards, and a non‐exhaustive set of examples of acquired experimental results are provided. For a consistent interpretation of the latter, the concepts brought forward in the literature considering the role of initial and final states of spectroscopic processes are outlined, with important consequences for quantitatively correct energy diagrams

Influence of substrate materials on nucleation and properties of iridium thin films grown by ALD

Ultra-thin metallic films are widely applied in optics and microelectronics. However, their properties differ significantly from the bulk material and depend on the substrate material. The nucleation, film growth, and layer properties of atomic layer deposited (ALD) iridium thin films are evaluated on silicon wafers, BK7, fused silica, SiO2 , TiO2 , Ta2O5 , Al2O3 , HfO2 , Ru, Cr, Mo, and graphite to understand the influence of various substrate materials. This comprehensive study was carried out using scanning electron and atomic force microscopy, X-ray reflectivity and diffraction, four-point probe resistivity and contact angle measurements, tape tests, and Auger electron spectroscopy. Within few ALD cycles, iridium islands occur on all substrates. Nevertheless, their size, shape, and distribution depend on the substrate. Ultra-thin (almost) closed Ir layers grow on a Ta2O5 seed layer after 100 cycles corresponding to about 5 nm film thickness. In contrast, the growth on Al2O3 and HfO2 is strongly inhibited. The iridium growth on silicon wafers is overall linear. On BK7, fused silica, SiO2 , TiO2 , Ta2O5 , Ru, Cr, and graphite, three different growth regimes are distinguishable. The surface free energy of the substrates correlates with their iridium nucleation delay. Our work, therefore, demonstrates that substrates can significantly tailor the properties of ultra-thin films

Frontier Orbital Degeneracy: A new Concept for Tailoring the Magnetic State in Organic Semiconductor Adsorbates

Kondo resonances in molecular adsorbates are an important building block for applications in the field of molecular spintronics. Here, we introduce the novel concept of using frontier orbital degeneracy for tailoring the magnetic state, which is demonstrated for the case of the organic semiconductor 1,4,5,8,9,11-Hexaazatriphenylenehexacarbonitrile (HATCN, C18N12) on Ag(111). Low-temperature scanning tunneling microscopy/spectroscopy (LT-STM/STS) measurements reveal the existence of two types of adsorbed HATCN molecules with distinctly different appearances and magnetic states, as evident from the presence or absence of an Abrikosov-Suhl-Kondo resonance. Our DFT results show that HATCN on Ag(111) supports two almost isoenergetic states, both with one excess electron transferred from the Ag surface, but with magnetic moments of either 0 or 0.65 uB. Therefore, even though all molecules undergo charge transfer of one electron from the Ag substrate, they exist in two different molecular magnetic states that resemble a free doublet or an entangled spin state. We explain how the origin of this behavior lies in the twofold degeneracy of the lowest unoccupied molecular orbitals of gas phase HATCN, lifted upon adsorption and charge-transfer from Ag(111). Our combined STM and DFT study introduces a new pathway to tailoring the magnetic state of molecular adsorbates on surfaces, with significant potential for spintronics and quantum information science

Impetuous CO2 release from eroding permafrost coasts

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Implications on zinc binding to S100A2

AbstractHuman S100A2 is an EF-hand calcium-binding S100 protein that is localized mainly in the nucleus and functions as tumor suppressor. In addition to Ca2+ S100A2 binds Zn2+ with a high affinity. Studies have been carried out to investigate whether Zn2+ acts as a regulatory ion for S100A2, as in the case of Ca2+. Using the method of competition with the Zn2+ chelator 4-(2-pyridylazo)-resorcinol, an apparent Kd of 25 nM has been determined for Zn2+ binding to S100A2. The affinity lies close to the range of intracellular free Zn2+ concentrations, suggesting that S100A2 is able to bind Zn2+ in the nucleus. Two Zn2+-binding sites have been identified using site directed mutagenesis and several spectroscopic techniques with Cd2+ and Co2+ as probes. In site 1 Zn2+ is bound by Cys21 and most likely by His 17. The binding of Zn2+ in site 2 induces the formation of a tetramer, whereby the Zn2+ is coordinated by Cys2 from each subunit. Remarkably, only binding of Zn2+ to site 2 substantially weakens the affinity of S100A2 for Ca2+. Analysis of the individual Ca2+-binding constants revealed that the Ca2+ affinity of one EF-hand is decreased about 3-fold, whereas the other EF-hand exhibits a 300-fold decrease in affinity. These findings imply that S100A2 is regulated by both Zn2+ and Ca2+, and suggest that Zn2+ might deactivate S100A2 by inhibiting response to intracellular Ca2+ signals

Stereotactic radiotherapy in the treatment of brain metastases

This thematic review is part of a larger, comparative dosimetric analysis of the evaluation of treatment plans created by different modulated intensity irradiation, which is delivered by means a linear accelerator for the treatment of multiple metastases in the brain. There is currently no consensus as to which method is dosimetrically better. A further study will be aimed at determining the dosimetric advantages of each irradiation technique to introduce additional certainty into the planning process

A mathematical model of the impact of forest fires on settlements

Статья посвящена проведению математического моделирования воздействия лесных пожаров на населенные пункты для определения безопасных расстояний от лесного массива до зданий. Подход к моделированию основан на использовании стандартных нестационарных двумерных уравнений сохранения, которые решаются численно при входных условиях, характерных для крупных лесных пожаров.The article is devoted to the mathematical modeling of the impact of forest fires on human settlements to determine the safe distance from the forest to the buildings. The modeling approach is based on the use of standard non-stationary two-dimensional conservation equations, which are solved numerically under the input conditions typical for large forest fires

Rapid CO2 release from eroding permafrost in seawater

Permafrost is thawing extensively due to climate warming. When permafrost thaws, previously frozen organic carbon (OC) is converted into carbon dioxide (CO2) or methane, leading to further warming. This process is included in models as gradual deepening of the seasonal non‐frozen layer. Yet, models neglect abrupt OC mobilization along rapidly eroding Arctic coastlines. We mimicked erosion in an experiment by incubating permafrost with seawater for an average Arctic open‐water season. We found that CO2 production from permafrost OC is as efficient in seawater as without. For each gram (dry weight) of eroding permafrost, up to 4.3 ± 1.0 mg CO2 will be released and 6.2 ± 1.2% of initial OC mineralized at 4 °C. Our results indicate that potentially large amounts of CO2 are produced along eroding permafrost coastlines, onshore and within nearshore waters. We conclude that coastal erosion could play an important role in carbon cycling and the climate system