Tuning the dispersion of 4f bands in the heavy-fermion material YbRh2Si2

Localized Yb 4f and itinerant Rh 4d states are subject to substantial hybridization effects in the heavy-fermion material YbRh₂Si₂. The proximity to the Fermi level and the high anisotropy in k space naturally raise questions regarding the role of these hybridization effects for the observed, unusual physical properties. Using angle-resolved photoemission spectroscopy (ARPES) we found that the non-dispersive behavior of the localized Yb f states is broken around the Γ point due to interaction with approaching Rh 4d bands. The intriguing point here is that the hybridization strength turns out to be systematically tunable by electron doping of the material. Gradual deposition of silver atoms onto the atomically clean, silicon terminated surface of YbRh₂Si₂ leads to transfer of Ag 5s charge into the Rh 4d bands. This substantially changes the energy overlap, and thus the hybridization strength, between the interacting Yb 4f and Rh 4d bands in the surface and subsurface region. The shown possibility to control the variation of the f-d hybridization at the surface of heavy-fermion materials may also be helpful for other ARPES studies on the diverse phenomena in electron-correlated materials.     

The role of hybridization on valence transitions in the spinless Falicov-Kimball model

The spinless Falicov-Kimball model with hybridization is studied in one dimension using small-cluster exact-diagonalization calculations. The resultant exact solutions are used to examine the f-state occupation n ^f as a function of f-level energy E _f, hybridization V and d-f interaction U. In addition, the phase diagram based on the finite-size scaling analysis of the single particle excitation energy is discussed both for the symmetric (E _f = 0) and unsymmetric (E _f ≠ 0) case. A number of remarkable results are found. (i) The f-electron occupation number as a function of E _f changes continuously, confirming renormalization-group results. No discontinuous transitions are observed at finite V. (ii) In the symmetric case the insulating state persists as the ground state for all nonzero V. (iii) Outside the symmetric point the hybridization stabilizes the metallic state for lower V and the insulating state for higher V. (iv) The metal-insulator transition takes place at V = V _c > 0. The values of the critical hybridization strength V _c are of order 10^?2.     

Isochromat spectroscopy on CePd3

Isochromat spectra from CePd₃ recorded at quantum energies of 9.7 and 72.7 eV are presented. The data obtained at 9.7 eV show three different peaks and are by and large identical to previously published data for a quantum energy of 1486 eV. Only two of those three peaks are present in the 72.7 eV spectrum. We conclude that the missing peak is bulk in origin and derives from a Ce5d-Pd4d hybridization leading to a Ce5d split off level from the filled Pd d-band.     

Breakdown of the one electron approximation for 4p core electron energy loss spectra in the rare earths

At high incident electron energies the 4p core electron energy loss features of clean La, Ce and Gd strongly resemble the corresponding XPS spectrum with evidence of strong 4p^-1 ? 4d^-2?f giant Coster-Kronig resonance in the “4p_{$\text{1}\text{2}$}” spectrum. The absence of charge transfer screening peaks in the $\text{4p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ loss of the oxides is attributed to localised 4p → 5d¹ excitation. As the primary energy approaches threshold, a satellite on the low energy side of the $\text{4p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ losses of La and Ce grows in intensity, due to excitations of multiples through non-dipole transitions.     

Angle-resolved photoemission spectroscopy study of the (101) surface of the Kondo insulator CeNiSn

The electronic structure of CeNiSn, which is considered a possible topological Kondo insulator, has been investigated by employing synchrotron radiation excited angle-resolved photoemission spectroscopy (ARPES). We have found that the easy cleavage plane in CeNiSn is (101), for which we have investigated the Fermi surface (FS) and band structures. The measured FS and ARPES for the (101) plane are described well by the calculated FS and band structures, obtained from the DFT calculations. The measured ARPES bands and photon energy map show that the metallic states crossing the Fermi level have the 3D nature, casting a negative suspicion for the existence of the topological surface states of the 2D character in CeNiSn. The Ce 4f Kondo resonance peak is observed in Ce 4d → 4f resonant photoemission spectroscopy, suggesting the importance of the Ce 4f electrons in determining the temperature-dependent topological electronic structure of CeNiSn.     

Electronic structure and magnetic properties of the compound CeCuIn

Magnetization, magnetic susceptibility, electrical resistivity, thermoelectric power and X-ray photoemission measurements were performed on a polycrystalline sample of CeCuIn. This compound crystallizes in a hexagonal structure of the ZrNiAl type. The magnetic data indicate that CeCuIn remains paramagnetic down to 1.9 K with a paramagnetic Curie temperature of −13 K and an effective magnetic moment equal to 2.5 μ_B. The electrical resistivity has metallic character, yet in the entire temperature range studied here, it is a strongly nonlinear function of temperature. The temperature dependence of the thermoelectric power is dominated by a small positive maximum near 76 K and a deep negative minimum at about 16 K. Above 150 K the thermopower exhibits a Mott's type behavior. The positive sign of the Seebeck coefficient in this temperature region indicates that the holes are dominant charge and heat carriers. The structure of Ce 3d_5/2 and Ce 3d_3/2 XPS spectra has been interpreted in terms of the Gunnarsson-Schönhammer theory. Three final-state contributions f⁰, f¹ and f² are clearly observed, which exhibit a spin-orbit splitting Δ_SO≈18.7 eV. The appearance of the 3d⁹f⁰ component is a clear evidence of the intermediate valence behavior of Ce. From the intensity ratio I(f⁰)/[I(f⁰)+I(f¹)+I(f²)] the 4f-occupation number is estimated to be 0.95. In turn, the ratio I(f²)/[I(f¹)+I(f²)]=0.08 yields a measure of the hybridization energy that is equal to 45 meV.     

Spectroscopic evidence of configuration-dependent hybridization in a cerium compound: CeRh3

Evidence is given for a configuration dependent hybridization in the spectroscopy of a strongly hybridized compound like CeRh₃. This is achieved by comparing the results of 4f inverse photoemission and Ce 3d core level spectroscopies to the predictions of the single impurity Anderson model (SIAM). This analysis shows that the SIAM is not able to quantitatively describe, within a single set of parameters, the results of both spectroscopies. A considerably better agreement with experiments is instead obtained when changes in the hybridization parameter are allowed in the different final states. This result suggests that the hybridization between f and band states strongly depends on the 4f configuration as theoretically predicted.     

Ce CORE level X-ray photoelectron spectroscopy of CeX2Si2 (X = Fe,Co, Ni and Cu)

Ce(3d) and (4d) core level XPS spectra of CeX = Fe, Co, Ni and Cu) suggest that the mean valence of Ce was as well as 4f hybridization strength decrease systematically from Fe to Cu. This observation is in agreement with the results of Bremstrahlung Isochromat Spectroscopy (BIS), but in disagreement with L_III-edge data reported earlier.     

Luminescence properties of Li6GdB3O9:Ce crystal fibers upon their excitation in the range of 4d → 4f core transitions

We have investigated UV luminescence with a subnanosecond time resolution of Li₆GdB₃O₉:Ce crystal fibers upon their ultrasoft X-ray selective excitation at 10 and 293 K in the range of 4d → 4f core transitions. We have revealed an intense fast-decaying subnanosecond luminescence component, which is caused by a high local density of electronic excitation and Auger core hole relaxation processes, and modulation of the luminescence excitation spectrum by an absorption band of the 4d–4f photoionization giant resonance in the energy range 135–160 eV.     

Configuration crossover in 4f substances under pressure

It is well established that in 4f substances the application of pressure tends to reduce the number of 4f electrons, so that if a configuration 4fⁿ is initially stable there may be a crossover to 4f^n?1 as the stable configuration at high pressures. We develop a simple theory of this configuration crossover, with particular emphasis on the questions of whether the crossover occurs discontinuously and whether a fractional-valence thermodynamic state, in which the individual 4f ions undergo rapid interconfiguration fluctuations, is stable near the crossover. The theory yields the 4f occupancy, which implies the main contribution to the Mössbauer isomer shift, and the pressure-volume relation. Model calculations are given for Ce metal and for the Sm monochalcogenides.     

Localized versus itinerant 5f electrons: A comparative study of USb and UO2

The near normal incidence reflectivity of USb single crystals has been measured for photon energies from 0.03 to 11 eV. An energy level scheme is derived. Comparison with the corresponding results for UO₂ reveals for USb a hybridization of the 5f and 6d wave functions and a delocalization of 5f electrons. An estimate of the free carrier concentration indicates that USb has a non integer number of f electrons.     

t−d excitons in the optical spectrum of semiconducting SmS and Sm1−xGdx alloys

Thermomodulation studies of the optical properties of Sm_1?xGd_xS alloys are presented for x ? 0.15. A new interpretation of the low energy absorption peaks as excitons, where a Sm 5d electron is bound to a localized hole in the 4f shell, is strongly suggested.     

Luminescence study of the 4f5d configuration of Nd in LiYF4, LiLuF4 and BaY2F8 crystals

Ultraviolet fluorescence of Nd³⁺ ions induced by triphotonic excitation process was studied in Nd-doped LiYF₄, LiLuF₄ and BaY₂F₈ crystals using a technique of time-resolved spectroscopy. The observed ultraviolet luminescence was due to transitions between the bottom of 4f²5d configuration and 4f³ states of Nd³⁺ ions. Narrow emission lines superposed to the broadband emissions were observed. A detailed analysis of luminescence spectrum revealed that the narrow emissions are due to parity and spin allowed radiative transitions from the Stark levels of ⁴K_11/2(5d) state created by the electrostatic interaction between the 5d electron and the two electrons of the 4f² configuration. The narrow emissions are related to the high spin state (S=3/2) which gives f-f characteristics to the f-d broadband emissions. The narrow emissions superposed to the wide emission correspond to 18%, 34% and 43% of the integrated broadband emission at 262 nm observed in LiYF₄, LiLuF₄ and BaY₂F₈ crystals, respectively. Although the 5d-4f² interaction is observed to be weaker than 5d-crystal field interaction, it is stronger enough to select only the radiative transitions from 4f²5d configuration to 4f³ states that preserves the total spin S=3/2.     

Photoemission from the valence bands of Ce(1 1 1) on W(1 1 0)

We report a photoelectron spectroscopic study of the valence bands of epitaxial Ce(1 1 1) films grown on W(1 1 0) at room temperature. The evolution of γ → α → γ like phase transition of Ce is observed with increasing Ce coverage and the valence-band structures of γ-like Ce film are determined. The 4f and 5d photoemission cross sections in the photon energy region from 20 eV to 130 eV are presented and discussed. A 5d-like surface state and a 6s band bottom are identified.     

Validity of the Anderson and Hubbard models for the description of metallic Ce and cerium heavy fermion compounds

The importance of the inclusion of inter-site f-f hybridization in electron structure calculations for metallic Ce and cerium heavy fermion compounds was studied. We demonstrate that for heavy-fermion systems such as cerium compound CeCu₂Si₂ f-f hybridization can be neglected and Anderson model application is well justified. On another hand for cerium metal f-f hybridization is strong enough to provide the contribution to hybridization function comparable to hybridization between 4f and itinerant electrons. We argue that in the case of Ce only the most general Hamiltonian combining the Hubbard and Anderson models should be used.     

High-resolution scanning tunneling microscopy and dI/dV map studies of peptidenucleic acid and fluorescein isothiocyanate

We used scanning tunneling microscopy (STM) to spatially map the local density of states of individual PNA molecules labeled with fluorescein isothiocyanate (FITC) on a Cu(1 1 1) surface. From the observed bias voltage dependences of the topographic height and the dI/dV map of FITC and individual PNA molecules, we confirmed that FITC and PNA have different electrical properties. We clearly differentiated the FITC and PNA molecules by mapping the density of states feature. This study shows that STM with the dI/dV map method is useful in FITC mapping.     

X-ray photoemission spectra of valence electrons in V3X and Nb3X compounds

The X-ray photoemission spectra (XPS) of the A15 type compounds V₃Au, Nb₃Os, Nb₃Ir, Nb₃Pt and Nb₃Au have been studied. The inner level binding energies of the different components and the valence electron distribution were measured. The Nb4d and the X5d energy bands of the Nb₃X compounds appear to be more and more separate with increasing atomic number of the X component. The comparison between the results from X-ray emission spectroscopy (XES) and X-ray photoelectron spectroscopy (XPS) of corresponding V₃X and Nb₃X compounds points out the similarity of their electronic structures.     

Thermopower of CeNi5 with strong f-electron instability: Band effects

Numerical calculations of the thermopower component S _d that is associated with the fine structure of the density of d states near the Fermi level are carried out for CeNi₅ and its La analog. The estimates, together with earlier experimental data on the transport coefficients in Ce(M _xNi_1?x )₅ solid solutions with M=Ga, Cu (0≤x≤0.4)), are used to analyze the behavior of the thermopower component S _f originating from the Ce valence instability. It is shown that as Ce crosses over from the state of its usual intermediate valence to the saturated-valence state, the feature near the Fermi energy, which represents a Lorentzian-shaped peak of the density of f states, transforms to a double-humped structure. The possibility of formation of a strongly correlated band of f states in Ce(M _xNi_1?x )₅ in the crossover to the Ce saturated-valence state, accompanied by the opening of a quasi-gap Δ ～ 400 K, is discussed.     

Special analytic properties of the amplitude for scattering on the Woods-Saxon potential

It is shown that the s-wave partial amplitude f(k) for scattering on the real-valued Woods-Saxon potential V(r)=?V ₀/[1+exp((r?R)/d)] has very special analytic properties: the trajectories of the poles of the function k cotδ [of the zeros of the amplitude f(k)] coincide with the lines of the dynamical singularities [spurious poles of f(k)], so that the zeros and the poles compensate each other. In contrast to what is obtained for Yukawa-like potentials, the scattering length does not vanish here at zero energy. The results reported in this article were obtained analytically under the assumption that exp(-R/d)?1. The problem of revealing the poles of the function k cotδ in a partial-wave analysis of neutron scattering on nuclei is discussed.     

The 4d auger,coster-kronig,and recombination spectra of the lanthanides

A complete set of electron-excited 4d-basedAuger spectra of the lanthanide metals from lanthanum to lutetium (except the unstable promethium) is presented, in both differential and integral forms. It is believed that the set is more representative of clean surfaces of the lanthanides than any published hitherto. With the help of binding energy and electron loss measurements made in this laboratory and elsewhere, values of the various possible Auger, Coster—Kronig, and direct recombination transition energies are calculated, and for each transition a “centre of gravity” is derived based on relative intensities of final state multiplets, electron occupation of core levels, etc. By using arguments based on trends in the spectra across the series, on theoretically and experimentally derived values of U_eff for the difference 4fⁿ⁺¹→4f^n?1, and on plausibility, values of U_eff for 4fⁿ→ 4f^n?2 as well as for the other final state hole pair configurations are allocated. The relaxed transition energies so calculated are then compared with the experimental energies, from which it is possible in most cases to make assignment of the spectral features to the various transitions. As a result it is found that there are some significant disagreements with the theoretical rates of McGuire for lanthanide free atoms. The reasons for these disagreements are discussed, and an empirical model based on effective 4f and 5d populations and on the restrictions imposed by spin alignment is used to resolve the differences qualitatively.