Quantum-well states at the surface of a heavy-fermion superconductor.

Two-dimensional electronic states at surfaces are often observed in simple wide-band metals such as Cu or Ag (refs. 1-4). Confinement by closed geometries at the nanometre scale, such as surface terraces, leads to quantized energy levels formed from the surface band, in stark contrast to the continuous energy dependence of bulk electron bands2,5-10. Their energy-level separation is typically hundreds of meV (refs. 3,6,11). In a distinct class of materials, strong electronic correlations lead to so-called heavy fermions with a strongly reduced bandwidth and exotic bulk ground states12,13. Quantum-well states in two-dimensional heavy fermions (2DHFs) remain, however, notoriously difficult to observe because of their tiny energy separation. Here we use millikelvin scanning tunnelling microscopy (STM) to study atomically flat terraces on U-terminated surfaces of the heavy-fermion superconductor URu2Si2, which exhibits a mysterious hidden-order (HO) state below 17.5 K (ref. 14). We observe 2DHFs made of 5f electrons with an effective mass 17 times the free electron mass. The 2DHFs form quantized states separated by a fraction of a meV and their level width is set by the interaction with correlated bulk states. Edge states on steps between terraces appear along one of the two in-plane directions, suggesting electronic symmetry breaking at the surface. Our results propose a new route to realize quantum-well states in strongly correlated quantum materials and to explore how these connect to the electronic environment.

Magneto-Optical Detection of the Orbital Hall Effect in Chromium.

The orbital Hall effect has been theoretically predicted but its direct observation is a challenge. Here, we report the magneto-optical detection of current-induced orbital accumulation at the surface of a light 3d transition metal, Cr. The orbital polarization is in-plane, transverse to the current direction, and scales linearly with current density, consistent with the orbital Hall effect. Comparing the thickness-dependent magneto-optical measurements with ab initio calculations, we estimate an orbital diffusion length in Cr of 6.6±0.6 nm.

Magnetism in AV_{3}Sb_{5} (A=Cs, Rb, and K): Origin and Consequences for the Strongly Correlated Phases.

The V-based kagome systems AV_{3}Sb_{5} (A=Cs, Rb, and K) are unique by virtue of the intricate interplay of nontrivial electronic structure, topology, and intriguing fermiology, rendering them to be a playground of many mutually dependent exotic phases like charge-order and superconductivity. Despite numerous recent studies, the interconnection of magnetism and other complex collective phenomena in these systems has yet not arrived at any conclusion. Using first-principles tools, we demonstrate that their electronic structures, complex fermiologies and phonon dispersions are strongly influenced by the interplay of dynamic electron correlations, nontrivial spin-polarization and spin-orbit coupling. An investigation of the first-principles-derived intersite magnetic exchanges with the complementary analysis of q dependence of the electronic response functions and the electron-phonon coupling indicate that the system conforms as a frustrated spin cluster, where the occurrence of the charge-order phase is intimately related to the mechanism of electron-phonon coupling, rather than the Fermi-surface nesting.

Coherent modulation of the electron temperature and electron-phonon couplings in a 2D material.

Ultrashort light pulses can selectively excite charges, spins, and phonons in materials, providing a powerful approach for manipulating their properties. Here we use femtosecond laser pulses to coherently manipulate the electron and phonon distributions, and their couplings, in the charge-density wave (CDW) material 1T-TaSe2 After exciting the material with a femtosecond pulse, fast spatial smearing of the laser-excited electrons launches a coherent lattice breathing mode, which in turn modulates the electron temperature. This finding is in contrast to all previous observations in multiple materials to date, where the electron temperature decreases monotonically via electron-phonon scattering. By tuning the laser fluence, the magnitude of the electron temperature modulation changes from ∼200 K in the case of weak excitation, to ∼1,000 K for strong laser excitation. We also observe a phase change of π in the electron temperature modulation at a critical fluence of 0.7 mJ/cm2, which suggests a switching of the dominant coupling mechanism between the coherent phonon and electrons. Our approach opens up routes for coherently manipulating the interactions and properties of two-dimensional and other quantum materials using light.

High-Pressure Synthesis of Magnetic Neodymium Polyhydrides.

Ongoing search for room-temperature superconductivity is inspired by the unique properties of the electron-phonon interaction in metal superhydrides. Encouraged by the recently found highest-TC superconductor fcc-LaH10, here we discover several superhydrides of another lanthanoid, neodymium. We identify three novel metallic Nd-H phases at pressures ranging from 85 to 135 GPa: I4/mmm-NdH4, C2/c-NdH7, and P63/mmc-NdH9, synthesized by laser-heating metal samples in NH3BH3 media for in situ generation of hydrogen. A lower trihydride Fm3̅m-NdH3 is found at pressures from 2 to 52 GPa. I4/mmm-NdH4 and C2/c-NdH7 are stable from 135 to 85 GPa, and P63/mmc-NdH9 is stable from 110 to 130 GPa. Measurements of the electrical resistance of NdH9 demonstrate a possible superconducting transition at ∼4.5 K in P63/mmc-NdH9. Our theoretical calculations predict that all of the neodymium hydrides have antiferromagnetic order at pressures below 150 GPa and represent one of the first discovered examples of strongly correlated superhydrides with large exchange spin-splitting in the electronic band structure (>450 meV). The critical Néel temperatures for new neodymium hydrides are estimated using the mean-field approximation to be about 4 K (NdH4), 251 K (NdH7), and 136 K (NdH9).

Surface-orientation- and ligand-dependent quenching of the spin magnetic moment of Co porphyrins adsorbed on Cu substrates.

Porphyrin molecules are particularly interesting candidates for spintronic applications due to their bonding flexibility, which allows to modify their properties substantially by the addition or transformation of ligands. Here, we investigate the electronic and magnetic properties of cobalt octaethylporphyrin (CoOEP), deposited on copper substrates with two distinct crystallographic surface orientations, Cu(100) and Cu(111), with X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD). A significant magnetic moment is present in the Co ions of the molecules deposited on Cu(100), but it is completely quenched on Cu(111). Heating the molecules on both substrates to 500 K induces a ring-closure reaction with cobalt tetrabenzoporphyrin (CoTBP) as reaction product. In these molecules, the magnetic moment is quenched on both surfaces. Our XMCD and XAS measurements suggest that the filling of the dz2 orbital leads to a non-integer valence state and causes the quench of the spin moments on all samples except CoOEP/Cu(100), where the molecular conformation induces variations to the ligand field that lift the quench. We further employ density functional theory calculations, supplemented with on-site Coulomb correlations (DFT+U), to study the adsorption of these spin-bearing molecules on the Cu substrates. Our calculations show that charge transfer from the Cu substrates as well as charge redistribution within the Co 3d orbitals lead to the filling of the Co minority spin dz2 orbital, causing a 'turning off' of the exchange splitting and quenching of the spin moment at the Co magnetic centers. Our investigations suggest that, by this mechanism, molecule-substrate interactions can be used to control the quenching of the magnetic moments of the adsorbed molecules.

Distinguishing attosecond electron-electron scattering and screening in transition metals.

Electron-electron interactions are the fastest processes in materials, occurring on femtosecond to attosecond timescales, depending on the electronic band structure of the material and the excitation energy. Such interactions can play a dominant role in light-induced processes such as nano-enhanced plasmonics and catalysis, light harvesting, or phase transitions. However, to date it has not been possible to experimentally distinguish fundamental electron interactions such as scattering and screening. Here, we use sequences of attosecond pulses to directly measure electron-electron interactions in different bands of different materials with both simple and complex Fermi surfaces. By extracting the time delays associated with photoemission we show that the lifetime of photoelectrons from the d band of Cu are longer by ∼100 as compared with those from the same band of Ni. We attribute this to the enhanced electron-electron scattering in the unfilled d band of Ni. Using theoretical modeling, we can extract the contributions of electron-electron scattering and screening in different bands of different materials with both simple and complex Fermi surfaces. Our results also show that screening influences high-energy photoelectrons (≈20 eV) significantly less than low-energy photoelectrons. As a result, high-energy photoelectrons can serve as a direct probe of spin-dependent electron-electron scattering by neglecting screening. This can then be applied to quantifying the contribution of electron interactions and screening to low-energy excitations near the Fermi level. The information derived here provides valuable and unique information for a host of quantum materials.

Revealing the Nature of the Ultrafast Magnetic Phase Transition in Ni by Correlating Extreme Ultraviolet Magneto-Optic and Photoemission Spectroscopies.

By correlating time- and angle-resolved photoemission and time-resolved transverse magneto-optical Kerr effect measurements, both at extreme ultraviolet wavelengths, we uncover the universal nature of the ultrafast photoinduced magnetic phase transition in Ni. This allows us to explain the ultrafast magnetic response of Ni at all laser fluences-from a small reduction of the magnetization at low laser fluences, to complete quenching at high laser fluences. Both probe methods exhibit the same demagnetization and recovery timescales. The spin system absorbs the energy required to proceed through a magnetic phase transition within 20 fs after the peak of the pump pulse. However, the spectroscopic signatures of demagnetization of the material appear only after ≈200 fs and the subsequent recovery of magnetization on timescales ranging from 500 fs to >70 ps. We also provide evidence of two competing channels with two distinct timescales in the recovery process that suggest the presence of coexisting phases in the material.

Bright circularly polarized soft X-ray high harmonics for X-ray magnetic circular dichroism.

We demonstrate, to our knowledge, the first bright circularly polarized high-harmonic beams in the soft X-ray region of the electromagnetic spectrum, and use them to implement X-ray magnetic circular dichroism measurements in a tabletop-scale setup. Using counterrotating circularly polarized laser fields at 1.3 and 0.79 µm, we generate circularly polarized harmonics with photon energies exceeding 160 eV. The harmonic spectra emerge as a sequence of closely spaced pairs of left and right circularly polarized peaks, with energies determined by conservation of energy and spin angular momentum. We explain the single-atom and macroscopic physics by identifying the dominant electron quantum trajectories and optimal phase-matching conditions. The first advanced phase-matched propagation simulations for circularly polarized harmonics reveal the influence of the finite phase-matching temporal window on the spectrum, as well as the unique polarization-shaped attosecond pulse train. Finally, we use, to our knowledge, the first tabletop X-ray magnetic circular dichroism measurements at the N4,5 absorption edges of Gd to validate the high degree of circularity, brightness, and stability of this light source. These results demonstrate the feasibility of manipulating the polarization, spectrum, and temporal shape of high harmonics in the soft X-ray region by manipulating the driving laser waveform.

Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides.

A systematic X-ray absorption study at actinide N6,7 (4f → 6d transitions) edges was performed for light-actinide oxides including data obtained for the first time for NpO2, PuO2, and UO3. The measurements were supported by ab initio calculations based on local-density-approximation with added 5f-5f Coulomb interaction (LDA+U). Improved energy resolution compared to common experiments at actinide L(2,3) (2p → 6d transitions) edges allowed us to resolve the major structures of the unoccupied 6d density of states (DOS) and estimate the crystal-field splittings in the 6d shell directly from the spectra of light-actinide dioxides. The measurements demonstrated an enhanced sensitivity of the N(6,7) spectral shape to changes in the compound crystal structure. For nonstoichiometric NpO(2-x), the filling of the entire band gap with Np 6d states was observed thus supporting a phase coexistence of Np metal and stoichiometric NpO2 which is in agreement with the tentative Np-O phase diagram.

Ab Initio Theory of Coherent Laser-Induced Magnetization in Metals.

We present the first materials specific ab initio theory of the magnetization induced by circularly polarized laser light in metals. Our calculations are based on nonlinear density matrix theory and include the effect of absorption. We show that the induced magnetization, commonly referred to as inverse Faraday effect, is strongly materials and frequency dependent, and demonstrate the existence of both spin and orbital induced magnetizations which exhibit a surprisingly different behavior. We show that for nonmagnetic metals (such as Cu, Au, Pd, Pt) and antiferromagnetic metals the induced magnetization is antisymmetric in the light's helicity, whereas for ferromagnetic metals (Fe, Co, Ni, FePt) the imparted magnetization is only asymmetric in the helicity. We compute effective optomagnetic fields that correspond to the induced magnetizations and provide guidelines for achieving all-optical helicity-dependent switching.

Unraveling the electronic structure, spin states, optical and vibrational spectra of malaria pigment.

A detailed knowledge of the electronic structure and magnetic and optical properties of hemozoin, the malaria pigment, is essential for the design of effective antimalarial drugs and malarial diagnosis. By employing state-of-the-art electronic structure calculations, we have performed an in-depth investigation of the malaria pigment. Specifically, molecular bond lengths and spin states of the two Fe(III) heme centers and their exchange interaction, the UV/Vis absorption spectrum, and the IR vibrational spectra were calculated and compared with available experimental data. Our density functional theory (DFT)-based calculations predict a singlet ground spin state that stems from an S=5/2 spin state on each of the Fe heme centers with a very weak antiferromagnetic exchange interaction between them. Our theoretical UV/Vis and IR spectra provide explanations for various spectroscopic studies of hemozoin and ß-hematin (a synthetic analogue of hemozoin). A good comparison of calculated and measured properties demonstrates the convincing unveiling of the electronic structure of the malaria pigment. Based on the predicted vibrational spectra, we propose a unique spectral band from the nuclear resonance vibrational spectroscopy (NRVS) results that could be used as a key fingerprint for malarial detection.

Real-time observation of non-equilibrium phonon-electron energy and angular momentum flow in laser-heated nickel.

Identifying the microscopic nature of non-equilibrium energy transfer mechanisms among electronic, spin, and lattice degrees of freedom is central to understanding ultrafast phenomena such as manipulating magnetism on the femtosecond timescale. Here, we use time- and angle-resolved photoemission spectroscopy to go beyond the often-used ensemble-averaged view of non-equilibrium dynamics in terms of quasiparticle temperature evolutions. We show for ferromagnetic Ni that the non-equilibrium electron and spin dynamics display pronounced variations with electron momentum, whereas the magnetic exchange interaction remains isotropic. This highlights the influence of lattice-mediated scattering processes and opens a pathway toward unraveling the still elusive microscopic mechanism of spin-lattice angular momentum transfer.

Optical control of 4f orbital state in rare-earth metals.

A change of orbital state alters the coupling between ions and their surroundings drastically. Orbital excitations are hence key to understand and control interaction of ions. Rare-earth elements with strong magneto-crystalline anisotropy (MCA) are important ingredients for magnetic devices. Thus, control of their localized 4f magnetic moments and anisotropy is one major challenge in ultrafast spin physics. With time-resolved x-ray absorption and resonant inelastic scattering experiments, we show for Tb metal that 4f-electronic excitations out of the ground-state multiplet occur after optical pumping. These excitations are driven by inelastic 5d-4f-electron scattering, altering the 4f-orbital state and consequently the MCA with important implications for magnetization dynamics in 4f-metals and more general for the excitation of localized electronic states in correlated materials.

Imaging the three-dimensional Fermi-surface pairing near the hidden-order transition in URu2Si2 using angle-resolved photoemission spectroscopy.

We report angle-resolved photoemission spectroscopy experiments probing deep into the hidden-order state of URu(2)Si(2), utilizing tunable photon energies with sufficient energy and momentum resolution to detect the near Fermi-surface (FS) behavior. Our results reveal (i) the full itinerancy of the 5f electrons, (ii) the crucial three-dimensional k-space nature of the FS and its critical nesting vectors, in good comparison with density-functional theory calculations, and (iii) the existence of hot-spot lines and pairing of states at the FS, leading to FS gapping in the hidden-order phase.

Ammonia coordination introducing a magnetic moment in an on-surface low-spin porphyrin.

Amazing ammonia: The molecular spin state of Ni(II) porphyrin, supported on a ferromagnetic Co surface, can be reversibly switched between spin-off (S = 0) and spin-on (S = 1) states upon coordination and decoordination of the gaseous ligand NH3, respectively (see picture). This finding clearly indicates the possible use of the system as a single-molecule-based magnetochemical sensor and in spintronics.

Evidence for a delocalization quantum phase transition without symmetry breaking in CeCoIn5.

The study of quantum phase transitions that are not clearly associated with broken symmetry is a major effort in condensed matter physics, particularly in regard to the problem of high-temperature superconductivity, for which such transitions are thought to underlie the mechanism of superconductivity itself. Here we argue that the putative quantum critical point in the prototypical unconventional superconductor CeCoIn5 is characterized by the delocalization of electrons in a transition that connects two Fermi surfaces of different volumes, with no apparent broken symmetry. Drawing on established theory of f-electron metals, we discuss an interpretation for such a transition that involves the fractionalization of spin and charge, a model that effectively describes the anomalous transport behavior we measured for the Hall effect.

Nonequilibrium sub-10 nm spin-wave soliton formation in FePt nanoparticles.

Magnetic nanoparticles such as FePt in the L10 phase are the bedrock of our current data storage technology. As the grains become smaller to keep up with technological demands, the superparamagnetic limit calls for materials with higher magnetocrystalline anisotropy. This, in turn, reduces the magnetic exchange length to just a few nanometers, enabling magnetic structures to be induced within the nanoparticles. Here, we describe the existence of spin-wave solitons, dynamic localized bound states of spin-wave excitations, in FePt nanoparticles. We show with time-resolved x-ray diffraction and micromagnetic modeling that spin-wave solitons of sub-10 nm sizes form out of the demagnetized state following femtosecond laser excitation. The measured soliton spin precession frequency of 0.1 THz positions this system as a platform to develop novel miniature devices.

Valence-band electronic structure of iron phthalocyanine: an experimental and theoretical photoelectron spectroscopy study.

The electronic structure of iron phthalocyanine (FePc) in the valence region was examined within a joint theoretical-experimental collaboration. Particular emphasis was placed on the determination of the energy position of the Fe 3d levels in proximity of the highest occupied molecular orbital (HOMO). Photoelectron spectroscopy (PES) measurements were performed on FePc in gas phase at several photon energies in the interval between 21 and 150 eV. Significant variations of the relative intensities were observed, indicating a different elemental and atomic orbital composition of the highest lying spectral features. The electronic structure of a single FePc molecule was first computed by quantum chemical calculations by means of density functional theory (DFT). The hybrid Becke 3-parameter, Lee, Yang and Parr (B3LYP) functional and the semilocal 1996 functional of Perdew, Burke and Ernzerhof (PBE) of the generalized gradient approximation (GGA-)type, exchange-correlation functionals were used. The DFT/B3LYP calculations find that the HOMO is a doubly occupied π-type orbital formed by the carbon 2p electrons, and the HOMO-1 is a mixing of carbon 2p and iron 3d electrons. In contrast, the DFT/PBE calculations find an iron 3d contribution in the HOMO. The experimental photoelectron spectra of the valence band taken at different energies were simulated by means of the Gelius model, taking into account the atomic subshell photoionization cross sections. Moreover, calculations of the electronic structure of FePc using the GGA+U method were performed, where the strong correlations of the Fe 3d electronic states were incorporated through the Hubbard model. Through a comparison with our quantum chemical calculations we find that the best agreement with the experimental results is obtained for a U(eff) value of 5 eV.

Frequency-Independent Terahertz Anomalous Hall Effect in DyCo5 , Co32 Fe68 , and Gd27 Fe73 Thin Films from DC to 40 THz.

The anomalous Hall effect (AHE) is a fundamental spintronic charge-to-charge-current conversion phenomenon and closely related to spin-to-charge-current conversion by the spin Hall effect. Future high-speed spintronic devices will crucially rely on such conversion phenomena at terahertz (THz) frequencies. Here, it is revealed that the AHE remains operative from DC up to 40 THz with a flat frequency response in thin films of three technologically relevant magnetic materials: DyCo5 , Co32 Fe68 , and Gd27 Fe73 . The frequency-dependent conductivity-tensor elements σxx and σyx  are measured, and good agreement with DC measurements is found. The experimental findings are fully consistent with ab initio calculations of σyx for CoFe and highlight the role of the large Drude scattering rate (≈100 THz) of metal thin films, which smears out any sharp spectral features of the THz AHE. Finally, it is found that the intrinsic contribution to the THz AHE dominates over the extrinsic mechanisms for the Co32 Fe68 sample. The results imply that the AHE and related effects such as the spin Hall effect are highly promising ingredients of future THz spintronic devices reliably operating from DC to 40 THz and beyond.