| 1. |
- Caputo, Marco, et al.
(författare)
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Charge Transfer and Orbital Reconstruction at an Organic-Oxide Interface
- 2023
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Ingår i: Nano Letters. - 1530-6984. ; 23:23, s. 11211-11218
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Tidskriftsartikel (refereegranskat)abstract
- The two-dimensional electron system (2DES) located at the surface of strontium titanate (STO) and at several other STO-based interfaces has been an established platform for the study of novel physical phenomena since its discovery. Here we report how the interfacing of STO and tetracyanoquinodimethane (TCNQ) results in a charge transfer that depletes the number of free carriers at the STO surface, with a strong impact on its electronic structure. Our study paves the way for efficient tuning of the electronic properties, which promises novel applications in the framework of oxide/organic-based electronics.
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| 2. |
- Gleißner, Robert, et al.
(författare)
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Role of Oxidation–Reduction Dynamics in the Application of Cu/ZnO-Based Catalysts
- 2023
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Ingår i: ACS Applied Nano Materials. - 2574-0970. ; 6:9, s. 8004-8016
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Tidskriftsartikel (refereegranskat)abstract
- We investigated Cu nanoparticles (NPs) on vicinal and basal ZnO supports to obtain an atomistic picture of the catalyst’s structure under in situ oxidizing and reducing conditions. The Cu/ZnO model catalysts were investigated at elevated gas pressures by high energy grazing incidence X-ray diffraction and ambient pressure X-ray photoelectron spectroscopy (AP-XPS). We find that the Cu nanoparticles are fully oxidized to Cu2O under atmospheric conditions at room temperature. As the nanoparticles swell during oxidation, they maintain their epitaxy on basal ZnO (000 ± 1) surfaces, whereas on the vicinal ZnO (101̅4) surface, the nanoparticles undergo a coherent tilt. We find that the oxidation process is fully reversible under H2 flow at 500 K, resulting in predominantly well-aligned nanoparticles on the basal surfaces, whereas the orientation of Cu NPs on vicinal ZnO was only partially restored. The analysis of the substrate crystal truncation rods evidences the stability of basal ZnO surfaces under all gas conditions. No Cu–Zn bulk alloy formation is observed. Under CO2 flow, no diffraction signal from the nanoparticles is detected, pointing to their completely disordered state. The AP-XPS results are in line with the formation of CuO. Scanning electron microscopy images show that massive mass transport has set in, leading to the formation of larger agglomerates.
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| 3. |
- Hohmann, Lea, et al.
(författare)
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Effect of Coadsorbed Sulfur on the Dehydrogenation of Naphthalene on Ni(111)
- 2023
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 128:1, s. 67-76
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Tidskriftsartikel (refereegranskat)abstract
- There are several difficulties when experimentally determined reaction mechanisms are applied from model systems to real catalysis. Besides the infamous pressure and material gaps, it is sometimes necessary to consider impurities in the real reactant feedstock that can act as promoters or catalyst poisons and alter the reaction path. In this study, the effect of sulfur on the dehydrogenation of naphthalene on Ni(111) is investigated by using X-ray photoelectron spectroscopy and scanning tunneling microscopy. Sulfur induces a (5 root 3 x 2) surface reconstruction, as previously reported in the literature. The sulfur does not have a strong effect on the dehydrogenation temperature of naphthalene. However, the presence of sulfur leads to a preferred formation of carbidic over graphitic carbon and a strong inhibition of carbon diffusion into the nickel bulk, which is one of the steps of destructive whisker carbon formation described in the catalysis literature.
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| 4. |
- Jonsson, Viktor, et al.
(författare)
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Photoelectron dispersion in metallic and insulating thin films
- 2021
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Ingår i: Physical Review Research. - : American Physical Society. - 2643-1564. ; 3:3
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Tidskriftsartikel (refereegranskat)abstract
- The underlying mechanism behind the metal-to-insulator transition in is still a topic of intense debate. The two leading theoretical interpretations associate the transition with either electron-lattice or electron-electron correlations. Novel experimental results are required to converge towards one of the two scenarios. Here we report on a temperature-dependent angle-resolved photoelectron study of thin films across the metal-to-insulator transition. The obtained experimental results are compared to density functional theory calculations. We find an overall energy shift and compression of the electronic band structure across the transition while the overall band topology is conserved. The results demonstrate the importance of electron-electron correlations in establishing the insulating state.
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| 5. |
- Koutsouflakis, Emmanouil, et al.
(författare)
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Metamagnetic transition and a loss of magnetic hysteresis caused by electron trapping in monolayers of single-molecule magnet Tb2@C79N
- 2022
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Ingår i: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3364 .- 2040-3372. ; 14:27, s. 9877-9892
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Tidskriftsartikel (refereegranskat)abstract
- Realization of stable spin states in surface-supported magnetic molecules is crucial for their applications in molecular spintronics, memory storage or quantum information processing. In this work, we studied the surface magnetism of dimetallo-azafullerene Tb2@C79N, showing a broad magnetic hysteresis in a bulk form. Surprisingly, monolayers of Tb2@C79N exhibited a completely different behavior, with the prevalence of a ground state with antiferromagnetic coupling at low magnetic field and a metamagnetic transition in the magnetic field of 2.5-4 T. Monolayers of Tb2@C79N were deposited onto Cu(111) and Au(111) by evaporation in ultra-high vacuum conditions, and their topography and electronic structure were characterized by scanning tunneling microscopy and spectroscopy (STM/STS). X-ray photoelectron spectroscopy (XPS), in combination with DFT studies, revealed that the nitrogen atom of the azafullerene cage tends to avoid metallic surfaces. Magnetic properties of the (sub)monolayers were then studied by X-ray magnetic circular dichroism (XMCD) at the Tb-M4,5 absorption edge. While in bulk powder samples Tb2@C79N behaves as a single-molecule magnet with ferromagnetically coupled magnetic moments and blocking of magnetization at 28 K, its monolayers exhibited a different ground state with antiferromagnetic coupling of Tb magnetic moments. To understand if this unexpected behavior is caused by a strong hybridization of fullerenes with metallic substrates, XMCD measurements were also performed for Tb2@C79N adsorbed on h-BN|Rh(111) and MgO|Ag(100). The co-existence of two forms of Tb2@C79N was found on these substrates as well, but magnetization curves showed narrow magnetic hysteresis detectable up to 25 K. The non-magnetic state of Tb2@C79N in monolayers is assigned to anionic Tb2@C79N− species with doubly-occupied Tb-Tb bonding orbital and antiferromagnetic coupling of the Tb moments. A charge transfer from the substrate or trapping of secondary electrons are discussed as a plausible origin of these species.
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| 6. |
- Lee, Wei Chuang, et al.
(författare)
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Monolayer calibration of endofullerenes with x-ray absorption from implanted keV ion doses
- 2024
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Ingår i: Journal of Vacuum Science & Technology. A. Vacuum, Surfaces, and Films. - : American Institute of Physics (AIP). - 0734-2101 .- 1520-8559. ; 42:2
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Tidskriftsartikel (refereegranskat)abstract
- X-ray absorption spectroscopy (XAS) has the highest sensitivity for chemical element detection on surfaces. With this approach, small amounts of lanthanide-containing endofullerene molecules (Ho3N@C80) have been measured by total electron yield at a low flux bending magnet beamline. The monolayer coverage is calibrated by extrapolating the signals of constant doses (3 x 1014 cm-2) of Ho ions implanted into SiO2 with energies between 2 and 115 keV. At room temperature, the Ho XAS spectra of the molecules and implanted ions indicate trivalent but not identical Ho ground states. Still, this approach demonstrates a way for calibration of small coverages of molecules containing open core-shell elements.
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| 7. |
- Marks, Kess, et al.
(författare)
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Investigation of the surface species during temperature dependent dehydrogenation of naphthalene on Ni(111)
- 2019
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 150:24
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Tidskriftsartikel (refereegranskat)abstract
- The temperature dependent dehydrogenation of naphthalene on Ni(111) has been investigated using vibrational sum-frequency generation spectroscopy, X-ray photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory with the aim of discerning the reaction mechanism and the intermediates on the surface. At 110 K, multiple layers of naphthalene adsorb on Ni(111); the first layer is a flat lying chemisorbed monolayer, whereas the next layer(s) consist of physisorbed naphthalene. The aromaticity of the carbon rings in the first layer is reduced due to bonding to the surface Ni-atoms. Heating at 200 K causes desorption of the multilayers. At 360 K, the chemisorbed naphthalene monolayer starts dehydrogenating and the geometry of the molecules changes as the dehydrogenated carbon atoms coordinate to the nickel surface; thus, the molecule tilts with respect to the surface, recovering some of its original aromaticity. This effect peaks at 400 K and coincides with hydrogen desorption. Increasing the temperature leads to further dehydrogenation and production of H-2 gas, as well as the formation of carbidic and graphitic surface carbon. Published under license by AIP Publishing.
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| 8. |
- Marks, Kess, 1987-, et al.
(författare)
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Naphthalene Dehydrogenation on Ni(111) in the Presence of Chemisorbed Oxygen and Nickel Oxide
- 2024
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Ingår i: Catalysts. - : MDPI AG. - 2073-4344. ; 14:2
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Tidskriftsartikel (refereegranskat)abstract
- Catalyst passivation through carbon poisoning is a common and costly problem as it reduces the lifetime and performance of the catalyst. Adding oxygen to the feed stream could reduce poisoning but may also affect the activity negatively. We have studied the dehydrogenation, decomposition, and desorption of naphthalene co-adsorbed with oxygen on Ni(111) by combining temperature-programmed desorption (TPD), sum frequency generation spectroscopy (SFG), photoelectron spectroscopy (PES), and density functional theory (DFT). Chemisorbed oxygen reduces the sticking of naphthalene and shifts H2 production and desorption to higher temperatures by blocking active Ni sites. Oxygen increases the production of CO and reduces carbon residues on the surface. Chemisorbed oxygen is readily removed when naphthalene is decomposed. Oxide passivates the surface and reduces the sticking coefficient. But it also increases the production of CO dramatically and reduces the carbon residues. Ni2O3 is more active than NiO.
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| 9. |
- Messing, Maria, et al.
(författare)
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Iron-based magnetic nanoparticles by spark ablation
- 2019
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Konferensbidrag (refereegranskat)abstract
- Magnetic nanoparticles have shown great potential for use in drug delivery and bioimaging applications and are prospective building blocks in future high-performing permanent magnets. Today, magnetic nanoparticles are most often produced in batches by chemical methods resulting in the risk of chemical impurities and production of vast amounts of chemical waste. Aerosol generation methods on the other hand, particularly spark ablation, are promising for future generation of magnetic nanoparticles since they are simple, fast, continuous, scalable, provide good control of size and composition, and offer the possibility to form alloys of material combinations not miscible on the macroscopic scale. High controllability is of utmost importance when generating magnetic nanoparticles since small deviations in size can significantly alter the magnetic coercivity. Also, the composition of the particles is of high significance since the magnetic properties can be completely transformed by changes in elemental composition or the oxidation state of the particle.In this work, we present the successful generation of monodisperse bimetallic FeCr and FeMn nanoparticles by spark ablation, and the results from the thorough characterization of individual particles with aerosol instruments, transmission electron microscopy, and synchrotron-based X-ray photoelectron spectroscopy. We demonstrate how the carrier gas can be used to dictate the oxidation and how to alternate between self-passivated and completely oxidized nanoparticles. We also show how the produced particles can be deposited to yield a low surface concentration which is critical for minimizing interparticle interactions during magnetic measurements. Finally, as a proof of concept, measurements using a magnetometer equipped with a SQUID on samples with different particle coverages are presented.
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| 10. |
- Muntwiler, Matthias, et al.
(författare)
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Surface science at the PEARL beamline of the Swiss Light Source
- 2017
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Ingår i: Journal of Synchrotron Radiation. - 0909-0495. ; 24:1, s. 354-366
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Tidskriftsartikel (refereegranskat)abstract
- The Photo-Emission and Atomic Resolution Laboratory (PEARL) is a new soft X-ray beamline and surface science laboratory at the Swiss Light Source. PEARL is dedicated to the structural characterization of local bonding geometry at surfaces and interfaces of novel materials, in particular of molecular adsorbates, nanostructured surfaces, and surfaces of complex materials. The main experimental techniques are soft X-ray photoelectron spectroscopy, photoelectron diffraction, and scanning tunneling microscopy (STM). Photoelectron diffraction in angle-scanned mode measures bonding angles of atoms near the emitter atom, and thus allows the orientation of small molecules on a substrate to be determined. In energy scanned mode it measures the distance between the emitter and neighboring atoms; for example, between adsorbate and substrate. STM provides complementary, real-space information, and is particularly useful for comparing the sample quality with reference measurements. In this article, the key features and measured performance data of the beamline and the experimental station are presented. As scientific examples, the adsorbate-substrate distance in hexagonal boron nitride on Ni(111), surface quantum well states in a metal-organic network of dicyano-anthracene on Cu(111), and circular dichroism in the photoelectron diffraction of Cu(111) are discussed.
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| 11. |
- Nowakowska, Sylwia, et al.
(författare)
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Adsorbate-Induced Modification of the Confining Barriers in a Quantum Box Array
- 2018
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Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 12:1, s. 768-778
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Tidskriftsartikel (refereegranskat)abstract
- Quantum devices depend on addressable elements, which can be modified separately and in their mutual interaction. Self-assembly at surfaces, for example, formation of a porous (metal-) organic network, provides an ideal way to manufacture arrays of identical quantum boxes, arising in this case from the confinement of the electronic (Shockley) surface state within the pores. We show that the electronic quantum box state as well as the interbox coupling can be modified locally to a varying extent by a selective choice of adsorbates, here C60, interacting with the barrier. In view of the wealth of differently acting adsorbates, this approach allows for engineering quantum states in on-surface network architectures.
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| 12. |
- Preger, Calle, et al.
(författare)
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Controlled Oxidation and Self-Passivation of Bimetallic Magnetic FeCr and FeMn Aerosol Nanoparticles
- 2019
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 123:26, s. 16083-16090
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Tidskriftsartikel (refereegranskat)abstract
- Nanoparticle generation by aerosol methods, particularly spark ablation, has high potential for creating new material combinations with tailored magnetic properties. By combining elements into complex alloyed nanoparticles and controlling their size and structure, different magnetic properties can be obtained. In combination with controlled deposition, to ensure nanoparticle separation, it is possible to minimize interparticle interactions and measure the intrinsic magnetic property of the nanoparticles. Most magnetic materials are highly sensitive to oxygen, and it is therefore crucial to both understand and control the oxidation of magnetic nanoparticles. In this study, we have successfully generated oxidized, bimetallic FeCr and FeMn nanoparticles by spark ablation in combination with a compaction step and thoroughly characterized individual particles with aerosol instruments, transmission electron microscopy and synchrotron-based X-ray photoelectron spectroscopy. The generated nanoparticles had an almost identical transition-metal ratio to the electrodes used as seed materials. Further, we demonstrate how the carrier gas can be used to dictate the oxidation and how to alternate between self-passivated and entirely oxidized nanoparticles. We also discuss the complexity of compacting alloyed nanoparticles consisting of elements with different vapor pressures and how this will affect the composition. This knowledge will further the understanding of design and generation of complex alloyed nanoparticles based on transition metals using aerosol methods, especially for the size regime where a compaction step is needed. As a proof of concept, measurements using a magnetometer equipped with a superconducting quantum interference device were performed on samples with different particle coverages. These measurements show that the magnetic properties could be explored for both high and low surface coverages, which open a way for studies where interparticle interactions can be systematically controlled.
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| 13. |
- Sassa, Yasmine, 1981, et al.
(författare)
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Kagome-like silicene: A novel exotic form of two-dimensional epitaxial silicon
- 2020
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Ingår i: Applied Surface Science. - : Elsevier BV. - 0169-4332 .- 1873-5584. ; 530
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Tidskriftsartikel (refereegranskat)abstract
- Since the discovery of graphene, intensive efforts have been made in search of novel two-dimensional (2D) materials. Decreasing the materials dimensionality to their ultimate thinness is a promising route to unveil new physical phenomena, and potentially improve the performance of devices. Among recent 2D materials, analogs of graphene, the group IV elements have attracted much attention for their unexpected and tunable physical properties. Depending on the growth conditions and substrates, several structures of silicene, germanene, and stanene can be formed. Here, we report the synthesis of a Kagome-like lattice of silicene on aluminum (1 1 1) substrates. We provide evidence of such an exotic 2D Si allotrope through scanning tunneling microscopy (STM) observations, high-resolution core-level (CL) and angle-resolved photoelectron spectroscopy (ARPES) measurements, along with Density Functional Theory calculations.
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| 14. |
- Tarasov, Artem V., et al.
(författare)
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Crystal electric field and properties of 4f magnetic moments at the surface of the rare-earth compound TbRh2Si2
- 2022
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Ingår i: Physical Review B. - 2469-9950. ; 106:15
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Tidskriftsartikel (refereegranskat)abstract
- The crystal electric field (CEF) plays an essential role in defining the magnetic properties of 4f materials. It forces the charge density of 4f electrons and the related magnetic moment to be oriented along a certain direction in the crystal. The CEF and related magnetic properties were widely studied in the past with focus on bulk of 4f materials, while their surfaces have not received much attention. By the example of the antiferromagnetic material TbRh2Si2 and using first-principles calculations and classical 4f angle-resolved photoemission (PE) measurements, we show how the CEF and related magnetic properties, linked with the orientation of 4f moments, are modified at the surface region. Precisely, we studied the CEF characteristics in individual Tb layers for Tb- and Si-terminated surfaces of TbRh2Si2. We show how strongly the CEF changes near the surface and how dramatically it influences the orientation of the 4f moments relative to the bulk. The instructive message of our study is that a rather valuable information about the CEF-related phenomena can be derived from the temperature dependence of 4f PE spectra. The presented methodology including the theoretical approach can be further applied to many other layered and quasi-2D rare-earth-based materials for unveiling their surface magnetic properties.
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| 15. |
- Tarasov, Artem V., et al.
(författare)
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Structural instability at the In-terminated surface of the heavy-fermion superconductor CeIrIn5
- 2022
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Ingår i: Surfaces and Interfaces. - : Elsevier BV. - 2468-0230. ; 32
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Tidskriftsartikel (refereegranskat)abstract
- Driven by reconstruction and relaxation, by the appearance of surface electron states and resonances, the surface properties and related temperature scales of strongly correlated f-materials may differ dramatically from those in the bulk. Applying low energy electron and photoelectron diffraction techniques, momentum-resolved photoelectron spectroscopy and ab initio calculations, we demonstrate that the In-terminated surface of the heavyfermion superconductor CeIrIn5 experiences a reconstruction with a (root 2v x root 2)R45 degrees ordered structure. The latter appears due to the displacement of In atoms with respect to the Ir sublattice. We show that the electronic structure and related properties of the reconstructed In surface differ remarkably from the unreconstructed case. Namely, the predicted surface states with Rashba-type spin splitting do not appear. Our results suggest surface instabilities in similar quasi-two-dimensional strongly correlated f-materials, for which surface reconstructions can be unveiled by means of diffraction techniques.
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| 16. |
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| 17. |
- Westerström, Rasmus, et al.
(författare)
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Surface Aligned Magnetic Moments and Hysteresis of an Endohedral Single-Molecule Magnet on a Metal
- 2015
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Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 114:8
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Tidskriftsartikel (refereegranskat)abstract
- The interaction between the endohedral unit in the single-molecule magnet Dy2ScN@C-80 and a rhodium (111) substrate leads to alignment of the Dy 4f orbitals. The resulting orientation of the Dy2ScN plane parallel to the surface is inferred from comparison of the angular anisotropy of x-ray absorption spectra and multiplet calculations in the corresponding ligand field. The x-ray magnetic circular dichroism is also angle dependent and signals strong magnetocrystalline anisotropy. This directly relates geometric and magnetic structure. Element specific magnetization curves from different coverages exhibit hysteresis at a sample temperature of similar to 4 K. From the measured hysteresis curves, we estimate the zero field remanence lifetime during x-ray exposure of a submonolayer to be about 30 seconds.
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| 18. |
- Westerström, Rasmus, et al.
(författare)
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Tunneling, remanence, and frustration in dysprosium-based endohedral single-molecule magnets
- 2014
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 89:6, s. 060406-
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Tidskriftsartikel (refereegranskat)abstract
- Paramagnetic atoms inside nanometer sized fullerenes realize robust, and chemically protected, spin systems. Changing the stoichiometry of the endohedral clusters results in a variety of magnetic ground states, as it is demonstrated for DynSc3-nN@C-80 (n = 1,2,3). All three exhibit distinct hysteresis and qualify as single-molecule magnets. In zero field the magnetization of n = 1 decays via quantum tunneling, while ferromagnetic coupling of the individual dysprosium moments results in remanence for Dy2ScN@C-80 and in a frustrated ground state for n = 3. The latter ground state turns out to be one of the simplest realizations of a frustrated, ferromagnetically coupled, system.
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