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- ItemMetallofullerene photoswitches driven by photoinduced fullerene-to-metal electron transfer(Cambridge : RSC, 2021) Zalibera, Michal; Ziegs, Frank; Schiemenz, Sandra; Dubrovin, Vasilii; Lubitz, Wolfgang; Savitsky, Anton; Deng, Shihu H.M.; Wang, Xue-Bin; Advoshenko, Stanislav M.; Popov, Alexey A.We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of YxSc3−xN@C80 (x = 0–3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S1–T1 gap decrease in this row. For Sc3N@C80, we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin–lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14N, 45Sc, and 89Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y3N to Sc3N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.
- ItemChiral Spin Liquid Ground State in YBaCo3FeO7(College Park, Md. : APS, 2022) Schweika, W.; Valldor, M.; Reim, J.D.; Rößler, U.K.A chiral spin liquid state is discovered in the highly frustrated, noncentrosymmetric swedenborgite compound YBaCo3FeO7, a layered kagome system of hexagonal symmetry, by advanced polarized neutron scattering from a single domain crystalline sample. The observed diffuse magnetic neutron scattering has an antisymmetric property that relates to its specific chirality, which consists of three cycloidal waves perpendicular to the c axis, forming an entity of cylindrical symmetry. Chirality and symmetry agree with relevant antisymmetric exchanges arising from broken spatial parity. Applying a Fourier analysis to the chiral interference pattern, with distinction between kagome sites and the connecting trigonal interlayer sites of threefold symmetry, the chiral spin correlation function is determined. Characteristic chiral waves originate from the trigonal sites and extend over several periods in the kagome planes. The chiral spin liquid is remarkably stable at low temperatures despite strong antiferromagnetic spin exchange. The observation raises a challenge, since the commonly accepted ground states in condensed matter either have crystalline long-range order or form a quantum liquid. We show that, within the classical theory of magnetic order, a disordered ground state may arise from chirality. The present scenario, with antisymmetric exchange acting as a frustrating gauge background that stabilizes local spin lumps, is similar to the avoided phase transition in coupled gauge and matter fields for subnuclear particles.
- ItemRobust metastable skyrmions with tunable size in the chiral magnet FePtMo3 N(Woodbury, NY : Inst., 2020) Sukhanov, A.S.; Heinemann, A.; Kautzsch, L.; Bocarsly, J.D.; Wilson, S.D.; Felser, C.; Inosov, D.S.The synthesis of new materials that can host magnetic skyrmions and their thorough experimental and theoretical characterization are essential for future technological applications. The β-Mn-type compound FePtMo3N is one such novel material that belongs to the chiral space group P4132, where the antisymmetric Dzyaloshinskii-Moriya interaction is allowed due to the absence of inversion symmetry. We report the results of small-angle neutron scattering (SANS) measurements of FePtMo3N and demonstrate that its magnetic ground state is a long-period spin helix with a Curie temperature of 222 K. The magnetic field-induced redistribution of the SANS intensity showed that the helical structure transforms to a lattice of skyrmions at ∼13 mT at temperatures just below TC. Our key observation is that the skyrmion state in FePtMo3N is robust against field cooling down to the lowest temperatures. Moreover, once the metastable state is prepared by field cooling, the skyrmion lattice exists even in zero field. Furthermore, we show that the skyrmion size in FePtMo3N exhibits high sensitivity to the sample temperature and can be continuously tuned between 120 and 210 nm. This offers different prospects in the control of topological properties of chiral magnets. © 2020 authors. Published by the American Physical Society.
- ItemMagnetic hysteresis and strong ferromagnetic coupling of sulfur-bridged Dy ions in clusterfullerene Dy2S@C82(Cambridge : RSC, 2020) Krylov, Denis; Velkos, Georgios; Chen, Chia-Hsiang; Büchner, Bernd; Kostanyan, Aram; Greber, Thomas; Avdoshenko, Stanislav M.; Popov, Alexey A.Two isomers of metallofullerene Dy2S@C82 with sulfur-bridged Dy ions exhibit broad magnetic hysteresis with sharp steps at sub-Kelvin temperature. Analysis of the level crossing events for different orientations of a magnetic field showed that even in powder samples, the hysteresis steps caused by quantum tunneling of magnetization can provide precise information on the strength of intramolecular Dy⋯Dy interactions. A comparison of different methods to determine the energy difference between ferromagnetic and antiferromagnetic states showed that sub-Kelvin hysteresis gives the most robust and reliable values. The ground state in Dy2S@C82 has ferromagnetic coupling of Dy magnetic moments, whereas the state with antiferromagnetic coupling in Cs and C3v cage isomers is 10.7 and 5.1 cm-1 higher, respectively. The value for the Cs isomer is among the highest found in metallofullerenes and is considerably larger than that reported in non-fullerene dinuclear molecular magnets. Magnetization relaxation times measured in zero magnetic field at sub-Kelvin temperatures tend to level off near 900 and 3200 s in Cs and C3v isomers. These times correspond to the quantum tunneling relaxation mechanism, in which the whole magnetic moment of the Dy2S@C82 molecule flips at once as a single entity. © the Partner Organisations.
- ItemPressure-driven magnetic moment collapse in the ground state of MnO(Milton Park : Taylor & Francis, 2007) Kasinathan, Deepa; Koepernik, K.; Pickett, W.E.The zero temperature Mott transition region in antiferromagnetic, spin S = 5/2 MnO is probed using the correlated band theory LSDA + U method. The first transition encountered is an insulator-insulator volume collapse within the rocksalt structure that is characterized by an unexpected Hund's rule violating 'spin-flip' moment collapse. This spin-flip to S = 1/2 takes fullest advantage of the anisotropy of the Coulomb repulsion, allowing gain in the kinetic energy (which increases with decreasing volume) while retaining a sizable amount of the magnetic exchange energy. While transition pressures vary with the interaction strength, the spin-flip state is robust over a range of interaction strengths and for both B1 and B8 structures.
- ItemCoupling of chiralities in spin and physical spaces: The Möbius ring as a case study(College Park : American Physical Society, 2015) Pylypovskyi, Oleksandr V.; Kravchuk, Volodymyr P.; Sheka, Denis D.; Makarov, Denys; Schmidt, Oliver G.; Gaididei, YuriWe show that the interaction of the magnetic subsystem of a curved magnet with the magnet curvature results in the coupling of a topologically nontrivial magnetization pattern and topology of the object. The mechanism of this coupling is explored and illustrated by an example of a ferromagnetic Möbius ring, where a topologically induced domain wall appears as a ground state in the case of strong easy-normal anisotropy. For the Möbius geometry, the curvilinear form of the exchange interaction produces an additional effective Dzyaloshinskii-like term which leads to the coupling of the magnetochirality of the domain wall and chirality of the Möbius ring. Two types of domain walls are found, transversal and longitudinal, which are oriented across and along the Möbius ring, respectively. In both cases, the effect of magnetochirality symmetry breaking is established. The dependence of the ground state of the Möbius ring on its geometrical parameters and on the value of the easy-normal anisotropy is explored numerically.
- ItemThermalization by a synthetic horizon(College Park, MD : APS, 2022) Mertens, Lotte; Moghaddam, Ali G.; Chernyavsky, Dmitry; Morice, Corentin; van den Brink, Jeroen; van Wezel, JasperSynthetic horizons in models for quantum matter provide an alternative route to explore fundamental questions of modern gravitational theory. Here we apply these concepts to the problem of emergence of thermal quantum states in the presence of a horizon, by studying ground-state thermalization due to instantaneous horizon creation in a gravitational setting and its condensed matter analog. By a sudden quench to position-dependent hopping amplitudes in a one-dimensional lattice model, we establish the emergence of a thermal state accompanying the formation of a synthetic horizon. The resulting temperature for long chains is shown to be identical to the corresponding Unruh temperature, provided that the postquench Hamiltonian matches the entanglement Hamiltonian of the prequench system. Based on detailed analysis of the outgoing radiation we formulate the conditions required for the synthetic horizon to behave as a purely thermal source, paving a way to explore this interplay of quantum-mechanical and gravitational aspects experimentally.
- ItemResonant inelastic x-ray incarnation of Young’s double-slit experiment(Washington : American Association for the Advancement of Science (A A A S), 2019) Revelli, A.; Moretti, Sala, M.; Monaco, G.; Becker, P.; Bohatý, L.; Hermanns, M.; Koethe, T.C.; Fröhlich, T.; Warzanowski, P.; Lorenz, T.; Streltsov, S.V.; van Loosdrecht, P.H.M.; Khomskii, D.I.; van den Brink, J.; Grüninger, M.Young’s archetypal double-slit experiment forms the basis for modern diffraction techniques: The elastic scattering of waves yields an interference pattern that captures the real-space structure. Here, we report on an inelastic incarnation of Young’s experiment and demonstrate that resonant inelastic x-ray scattering (RIXS) measures interference patterns, which reveal the symmetry and character of electronic excited states in the same way as elastic scattering does for the ground state. A prototypical example is provided by the quasi-molecular electronic structure of insulating Ba 3 CeIr 2 O 9 with structural Ir dimers and strong spin-orbit coupling. The double “slits” in this resonant experiment are the highly localized core levels of the two Ir atoms within a dimer. The clear double-slit-type sinusoidal interference patterns that we observe allow us to characterize the electronic excitations, demonstrating the power of RIXS interferometry to unravel the electronic structure of solids containing, e.g., dimers, trimers, ladders, or other superstructures.