2019, Bläsing, Kevin, Labbow, Rene, Michalik, Dirk, Reiß, Fabian, Schul, Axel, Villinger, Alexander, Walker, Svenja

Attempts have been made to prepare salts with the labile tris(trimethylsilyl)chalconium ions, [(Me3Si)3E]+ (E=O, S), by reacting [Me3Si-H-SiMe3][B(C6F5)4] and Me3Si[CB] (CB−=carborate=[CHB11H5Cl6]−, [CHB11Cl11]−) with Me3Si-E-SiMe3. In the reaction of Me3Si-O-SiMe3 with [Me3Si-H-SiMe3][B(C6F5)4], a ligand exchange was observed in the [Me3Si-H-SiMe3]+ cation leading to the surprising formation of the persilylated [(Me3Si)2(Me2(H)Si)O]+ oxonium ion in a formal [Me2(H)Si]+ instead of the desired [Me3Si]+ transfer reaction. In contrast, the expected homoleptic persilylated [(Me3Si)3S]+ ion was formed and isolated as [B(C6F5)4]− and [CB]− salt, when Me3Si-S-SiMe3 was treated with either [Me3Si-H-SiMe3][B(C6F5)4] or Me3Si[CB]. However, the addition of Me3Si[CB] to Me3Si-O-SiMe3 unexpectedly led to the release of Me4Si with simultaneous formation of a cyclic dioxonium dication of the type [Me3Si-μO-SiMe2]2[CB]2 in an anion-mediated reaction. DFT studies on structure, bonding and thermodynamics of the [(Me3Si)3E]+ and [(Me3Si)2(Me2(H)Si)E]+ ion formation are presented as well as mechanistic investigations on the template-driven transformation of the [(Me3Si)3E]+ ion into a cyclic dichalconium dication [Me3Si-μE-SiMe2]22+. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

2017, Landstorfer, Manuel

Consistent boundary conditions for electrochemical interfaces, which cover double layer charging, pseudo-capacitive effects and transfer reactions, are of high demand in electrochemistry and adjacent disciplines. Mathematical modeling and optimization of electrochemical systems is a strongly emerging approach to reduce cost and increase efficiency of super-capacitors, batteries, fuel cells, and electro-catalysis. However, many mathematical models which are used to describe such systems lack a real predictive value. Origin of this shortcoming is the usage of oversimplified boundary conditions. In this work we derive the boundary conditions for some general electrode-electrolyte interface based on non-equilibrium thermodynamics for volumes and surfaces. The resulting equations are widely applicable and cover also tangential transport. The general framework is then applied to a specific material model which allows the deduction of a current-voltage relation and thus a comparison to experimental data. Some simplified 1D examples show the range of applicability of the new approach.

2015, Arabi-Hashemi, A., Witte, R., Lotnyk, A., Brand, R.A., Setzer, A., Esquinazi, P., Hahn, H., Averback, R.S., Mayr, S.G.

Control of multi-martensite phase transformations and physical properties constitute greatly unresolved challenges in Fe7Pd3-based ferromagnetic shape memory alloys. Single crystalline Fe7Pd3 thin films reveal an austenite to martensite phase transformation, continuously ranging from the face-centered cubic (fcc) to the face-centered tetragonal (fct) and body-centered cubic (bcc) phases upon irradiation with 1.8 MeV Kr+ ions. Within the present contribution, we explore this scenario within a comprehensive experimental study: employing atomic force microscopy (AFM) and high resolution transmission electron microscopy (HR-TEM), we first clarify the crystallography of the ion-irradiation-induced austenite $\Rightarrow $ martensite and inter-martensite transitions, explore the multi-variant martensite structures with c-a twinning and unravel a very gradual transition between variants at twin boundaries. Accompanying magnetic properties, addressed locally and globally, are characterized by an increasing saturation magnetization from fcc to bcc, while coercivity and remanence are demonstrated to be governed by magnetocrystalline anisotropy and ion-irradiation-induced defect density, respectively. Based on reversibility of ion-irradiation-induced materials changes due to annealing treatment and a conversion electron Mößbauer spectroscopy (CEMS) study to address changes in order, a quantitative defect-based physical picture of ion-irradiation-induced austenite ⇔ martensite transformation in Fe7Pd3 is developed. The presented concepts thus pave the way for ion-irradiation-assisted optimization strategies for tailored functional alloys.

2014, Müller, A., Meyer, J., Paumer, T., Pompe, T.

A cell's morphology is intricately regulated by microenvironmental cues and intracellular feedback signals. Besides biochemical factors, cell fate can be influenced by the mechanics and geometry of the surrounding matrix. The latter point was addressed herein, by studying cell adhesion on two-dimensional micropatterns. Endothelial cells were grown on maleic acid copolymer surfaces structured with stripes of fibronectin by microcontact printing. Experiments showed a biphasic behaviour of actin stress fibre spacing in dependence on the stripe width with a critical size of approx. 15 μm. In a concurrent modelling effort, cells on stripes were simulated as droplet-like structures, including variations of interfacial energy, total volume and dimensions of the nucleus. A biphasic behaviour with regard to cell morphology and area was found, triggered by the minimum of interfacial energy, with the phase transition occurring at a critical stripe width close to the critical stripe width found in the cell experiment. The correlation of experiment and simulation suggests a possible mechanism of the cytoskeletal rearrangements based on interfacial energy arguments.

2014, Ando, H., Fingerhut, B.P., Dorfman, K.E., Biggs, J.D., Mukamel, S.

Cyclobutane thymine dimer, one of the major lesions in DNA formed by exposure to UV sunlight, is repaired in a photoreactivation process, which is essential to maintain life. The molecular mechanism of the central step, i.e., intradimer C-C bond splitting, still remains an open question. In a simulation study, we demonstrate how the time evolution of characteristic marker bands (C=O and C=C/C-C stretch vibrations) of cyclobutane thymine dimer and thymine dinucleotide radical anion, thymidylyl(3′→5′)-thymidine, can be directly probed with femtosecond stimulated Raman spectroscopy (FSRS). We construct a DFT(M05-2X) potential energy surface with two minor barriers for the intradimer C5-C′5 splitting and a main barrier for the C6-C′6 splitting, and identify the appearance of two C5=C6 stretch vibrations due to the C6-C′6 splitting as a spectroscopic signature of the underlying bond splitting mechanism. The sequential mechanism shows only absorptive features in the simulated FSRS signals, whereas the fast concerted mechanism shows characteristic dispersive line shapes. (Figure Presented).

2012, Forkel, Matthias, Thonicke, Kirsten, Beer, Christian, Cramer, Wolfgang, Bartalev, Sergey, Schmullius, Christiane

Wildfires are a natural and important element in the functioning of boreal forests. However, in some years, fires with extreme spread and severity occur. Such severe fires can degrade the forest, affect human values, emit huge amounts of carbon and aerosols and alter the land surface albedo. Usually, wind, slope and dry air conditions have been recognized as factors determining fire spread. Here we identify surface moisture as an additional important driving factor for the evolution of extreme fire events in the Baikal region. An area of 127 000 km2 burned in this region in 2003, a large part of it in regions underlain by permafrost. Analyses of satellite data for 2002–2009 indicate that previous-summer surface moisture is a better predictor for burned area than precipitation anomalies or fire weather indices for larch forests with continuous permafrost. Our analysis advances the understanding of complex interactions between the atmosphere, vegetation and soil, and how coupled mechanisms can lead to extreme events. These findings emphasize the importance of a mechanistic coupling of soil thermodynamics, hydrology, vegetation functioning, and fire activity in Earth system models for projecting climate change impacts over the next century.

2022, Ćwik, Jacek, Koshkid’ko, Yurii, Nenkov, Konstantin, Tereshina-Chitrova, Evgenia, Małecka, Małgorzata, Weise, Bruno, Kowalska, Karolina

To date, significant efforts have been put into searching for materials with advanced magnetocaloric properties which show promise as refrigerants and permit realization of efficient cooling. The present study, by an example of Ho1−xErxNi2, develops the concept of magnetocaloric efficiency in the rare-earth Laves-phase compounds. Based on the magneto-thermodynamic properties, their potentiality as components of magnetocaloric composites is illustrated. The determined regularities in the behaviour of the heat capacity, magnetic entropy change, and adiabatic temperature change of the system substantiate reaching high magnetocaloric potentials in a desired temperature range. For the Ho1−xErxNi2 solid solutions, we simulate optimal molar ratios and construct the composites used in magnetic refrigerators performing an Ericsson cycle at low temperatures. The tailored magnetocaloric characteristics are designed and efficient procedures for their manufacturing are developed. Our calculations based on the real empirical data are very promising and open avenue to further experimental studies. Systems showing large magnetocaloric effect (MCE) at low temperatures are of importance due to their potential utilization in refrigeration for gas liquefaction.

2019, Vágner, Petr, Guhlke, Clemens, Miloš, Vojtěch, Müller, Rüdiger, Fuhrmann, Jürgen

A continuum model for yttria-stabilized zirconia (YSZ) in the framework of non-equilibrium thermodynamics is developed. Particular attention is given to (i) modeling of the YSZ-metal-gas triple phase boundary, (ii) incorporation of the lattice structure and immobile oxide ions within the free energy model and (iii) surface reactions. A finite volume discretization method based on modified Scharfetter-Gummel fluxes is derived in order to perform numerical simulations. The model is used to study the impact of yttria and immobile oxide ions on the structure of the charged boundary layer and the double layer capacitance. Cyclic voltammograms of an air-half cell are simulated to study the effect of parameter variations on surface reactions, adsorption and anion diffusion. © 2019, The Author(s).

2020, Hernandez, J.-A., Morard, G., Guarguaglini, M., Alonso-Mori, R., Benuzzi-Mounaix, A., Bolis, R., Fiquet, G., Galtier, E., Gleason, A.E., Glenzer, S., Guyot, F., Ko, B., Lee, H.J., Mao, W.L., Nagler, B., Ozaki, N., Schuster, A.K., Shim, S.H., Vinci, T., Ravasio, A.

We report in situ structural measurements of shock-compressed single crystal orthoenstatite up to 337 ± 55 GPa on the Hugoniot, obtained by coupling ultrafast X-ray diffraction to laser-driven shock compression. Shock compression induces a disordering of the crystalline structure evidenced by the appearance of a diffuse X-ray diffraction signal at nanosecond timescales at 80 ± 13 GPa on the Hugoniot, well below the equilibrium melting pressure (>170 GPa). The formation of bridgmanite and post-perovskite have been indirectly reported in microsecond-scale plate-impact experiments. Therefore, we interpret the high-pressure disordered state we observed at nanosecond scale as an intermediate structure from which bridgmanite and post-perovskite crystallize at longer timescales. This evidence of a disordered structure of MgSiO3 on the Hugoniot indicates that the degree of polymerization of silicates is a key parameter to constrain the actual thermodynamics of shocks in natural environments. © 2020. The Authors.

2013, Brambila, D.S., Fratalocchi, A.

By employing a nonlinear quantum kicked rotor model, we investigate the transport of energy in multidimensional quantum chaos. This problem has profound implications in many fields of science ranging from Anderson localization to time reversal of classical and quantum waves. We begin our analysis with a series of parallel numerical simulations, whose results show an unexpected and anomalous behavior. We tackle the problem by a fully analytical approach characterized by Lie groups and solitons theory, demonstrating the existence of a universal, nonlinearly-enhanced diffusion of the energy in the system, which is entirely sustained by soliton waves. Numerical simulations, performed with different models, show a perfect agreement with universal predictions. A realistic experiment is discussed in two dimensional dipolar Bose-Einstein-Condensates (BEC). Besides the obvious implications at the fundamental level, our results show that solitons can form the building block for the realization of new systems for the enhanced transport of matter.