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- ItemA selective route to aryl-triphosphiranes and their titanocene-induced fragmentation(Cambridge : RSC, 2019) Schumann, André; Reiß, Fabian; Jiao, Haijun; Rabeah, Jabor; Siewert, Jan-Erik; Krummenacher, Ivo; Braunschweig, Holger; Hering-Junghans, ChristianTriphosphiranes are three-membered phosphorus cycles and their fundamental reactivity has been studied in recent decades. We recently developed a high-yielding, selective synthesis for various aryl-substituted triphosphiranes. Variation of the reaction conditions in combination with theoretical studies helped to rationalize the formation of these homoleptic phosphorus ring systems and highly reactive intermediates could be isolated. In addition we showed that a titanocene synthon [Cp2Ti(btmsa)] facilitates the selective conversion of these triphosphiranes into titanocene diphosphene complexes. This unexpected reactivity mode was further studied theoretically and experimental evidence is presented for the proposed reaction mechanism. This journal is © The Royal Society of Chemistry.
- ItemConfined crystals of the smallest phase-change material(Washington, DC : American Chemical Society, 2013) Giusca, C.E.; Stolojan, V.; Sloan, J.; Börrnert, F.; Shiozawa, H.; Sader, K.; Rümmeli, M.H.; Büchner, B.; Silva, S.R.P.The demand for high-density memory in tandem with limitations imposed by the minimum feature size of current storage devices has created a need for new materials that can store information in smaller volumes than currently possible. Successfully employed in commercial optical data storage products, phase-change materials, that can reversibly and rapidly change from an amorphous phase to a crystalline phase when subject to heating or cooling have been identified for the development of the next generation electronic memories. There are limitations to the miniaturization of these devices due to current synthesis and theoretical considerations that place a lower limit of 2 nm on the minimum bit size, below which the material does not transform in the structural phase. We show here that by using carbon nanotubes of less than 2 nm diameter as templates phase-change nanowires confined to their smallest conceivable scale are obtained. Contrary to previous experimental evidence and theoretical expectations, the nanowires are found to crystallize at this scale and display amorphous-to-crystalline phase changes, fulfilling an important prerequisite of a memory element. We show evidence for the smallest phase-change material, extending thus the size limit to explore phase-change memory devices at extreme scales.
- ItemEvidence for Efficient Pathway to Produce Slow Electrons by Ground-state Dication in Clusters(Bristol : IOP Publ., 2017) You, Daehyun; Fukuzawa, Hironobu; Sakakibara, Yuta; Takanashi, Tsukasa; Ito, Yuta; Maliyar, Gianluigi G.; Motomura, Koji; Nagaya, Kiyonobu; Nishiyama, Toshiyuki; Asa, Kazuki; Sato, Yuhiro; Saito, Norio; Oura, Masaki; Schöffler, Markus; Kastirke, Gregor; Hergenhahn, Uwe; Stumpf, Vasili; Gohkberg, Kirill; Kuleff, Alexander I.; Cederbaum, Lorenz S.; Ueda, KiyoshiWe present an experimental evidence for a so-far unobserved, but potentially very important step relaxation cascades following inner-shell ionization of a composite system: Multiply charged ionic states created after Auger decay may be neutralized by electron transfer from a neighboring species, producing at the same time a low-energy free electron. This electron transfer-mediated decay (ETMD) called process is effective even after Auger decay into the dicationic ground state. Here, we report the ETMD of Ne2+ produced after Ne 1s photoionization in Ne-Kr mixed clusters.
- ItemQuantifying Rate-and Temperature-Dependent Molecular Damage in Elastomer Fracture(College Park, Md. : APS, 2020) Slootman, Juliette; Waltz, Victoria; Yeh, C. Joshua; Baumann, Christoph; Göstl, Robert; Comtet, Jean; Creton, CostantinoElastomers are highly valued soft materials finding many applications in the engineering and biomedical fields for their ability to stretch reversibly to large deformations. Yet their maximum extensibility is limited by the occurrence of fracture, which is currently still poorly understood. Because of a lack of experimental evidence, current physical models of elastomer fracture describe the rate and temperature dependence of the fracture energy as being solely due to viscoelastic friction, with chemical bond scission at the crack tip assumed to remain constant. Here, by coupling new fluorogenic mechanochemistry with quantitative confocal microscopy mapping, we are able to quantitatively detect, with high spatial resolution and sensitivity, the scission of covalent bonds as ordinary elastomers fracture at different strain rates and temperatures. Our measurements reveal that, in simple networks, bond scission, far from being restricted to a constant level near the crack plane, can both be delocalized over up to hundreds of micrometers and increase by a factor of 100, depending on the temperature and stretch rate. These observations, permitted by the high fluorescence and stability of the mechanophore, point to an intricate coupling between strain-rate-dependent viscous dissipation and strain-dependent irreversible network scission. These findings paint an entirely novel picture of fracture in soft materials, where energy dissipated by covalent bond scission accounts for a much larger fraction of the total fracture energy than previously believed. Our results pioneer the sensitive, quantitative, and spatially resolved detection of bond scission to assess material damage in a variety of soft materials and their applications. © 2020 authors. Published by the American Physical Society.
- ItemThe magneto-optical gradient effect in an exchange-biased thin film: Experimental evidence for classical diffraction theory(Milton Park : Taylor & Francis, 2010) Schäfer, R.; Hamann, C.; McCord, J.; Schultz, L.; Kamberský, V.The magneto-optical gradient effect decorates the boundaries of in-plane domains even at perpendicular incidence of light in an optical polarization microscope. For its explanation, the classical magneto-optical diffraction theory was previously used to derive the effect from the same gyrotropic interaction as the Kerr effect. In order to explain the symmetry of the experimentally observed contrast on bulk ferromagnetic crystals, planar as well as perpendicular subsurface gradients in the magnetization had to be assumed. This was particularly needed when the surface magnetizations in neighboring domains pointed head-on and a gradient contrast appeared also in conditions of vanishing gyrotropic interaction at the surface. The gradient contrast in such conditions should not appear in very thin films where perpendicular magnetization gradients are not enforced by reduction of magnetostatic energy. Here we present the first experimental confirmation of this expectation, thus closing an experimental gap in verifying the predictions of the diffraction theory.
- ItemNanoscale magneto-structural coupling in as-deposited and freestanding single-crystalline Fe7Pd3 ferromagnetic shape memory alloy thin films(Abingdon : Taylor & Francis, 2013) Landgraf, A.; Jakob, A.M.; Ma, Y.; Mayr, S.G.Ferromagnetic shape memory alloys are characterized by strong magneto-mechanical coupling occurring at the atomic scale causing large magnetically inducible strains at the macroscopic level. Employing combined atomic and magnetic force microscopy studies at variable temperature, we systematically explore the relation between the magnetic domain pattern and the underlying structure for as-deposited and freestanding single-crystalline Fe7Pd3 thin films across the martensite-austenite transition. We find experimental evidence that magnetic domain appearance is strongly affected by the presence and absence of nanotwinning. While the martensite-austenite transition upon temperature variation of as-deposited films is clearly reflected in topography by the presence and absence of a characteristic surface corrugation pattern, the magnetic domain pattern is hardly affected. These findings are discussed considering the impact of significant thermal stresses arising in the austenite phase. Freestanding martensitic films reveal a hierarchical structure of micro- and nanotwinning. The associated domain organization appears more complex, since the dominance of magnetic energy contributors alters within this length scale regime.
- ItemUltrafast optically induced spin transfer in ferromagnetic alloys(Washington, DC [u.a.] : Assoc., 2020) Hofherr, M.; Häuser, S.; Dewhurst, J.K.; Tengdin, P.; Sakshath, S.; Nembach, H.T.; Weber, S.T.; Shaw, J.M.; Silva, T.J.; Kapteyn, H.C.; Cinchetti, M.; Rethfeld, B.; Murnane, M.M.; Steil, D.; Stadtmüller, B.; Sharma, S.; Aeschlimann, M.; Mathias, S.The vision of using light to manipulate electronic and spin excitations in materials on their fundamental time and length scales requires new approaches in experiment and theory to observe and understand these excitations. The ultimate speed limit for all-optical manipulation requires control schemes for which the electronic or magnetic subsystems of the materials are coherently manipulated on the time scale of the laser excitation pulse. In our work, we provide experimental evidence of such a direct, ultrafast, and coherent spin transfer between two magnetic subsystems of an alloy of Fe and Ni. Our experimental findings are fully supported by time-dependent density functional theory simulations and, hence, suggest the possibility of coherently controlling spin dynamics on subfemtosecond time scales, i.e., the birth of the research area of attomagnetism.