Correlation between ground state and orbital anisotropy in heavy fermion materials.

The interplay of structural, orbital, charge, and spin degrees of freedom is at the heart of many emergent phenomena, including superconductivity. Unraveling the underlying forces of such novel phases is a great challenge because it not only requires understanding each of these degrees of freedom, it also involves accounting for the interplay between them. Cerium-based heavy fermion compounds are an ideal playground for investigating these interdependencies, and we present evidence for a correlation between orbital anisotropy and the ground states in a representative family of materials. We have measured the 4f crystal-electric field ground-state wave functions of the strongly correlated materials CeRh1-xIrxIn5 with great accuracy using linear polarization-dependent soft X-ray absorption spectroscopy. These measurements show that these wave functions correlate with the ground-state properties of the substitution series, which covers long-range antiferromagnetic order, unconventional superconductivity, and coexistence of these two states.

Synthesis, structural characterization, and physical properties of the early rare-earth metal digermanides REGe(2-x) (x ≈ 1/4) [RE = La-Nd, Sm]. A case study of commensurately and incommensurately modulated structures.

Rare-earth metal germanides with the general formula RE(4)Ge(7) (RE = La, Ce, Pr, Nd, Sm) have been synthesized using the In-flux technique. Their structures have been established from single-crystal and powder X-ray diffraction, and the structural elucidation has been aided by electron diffraction. These compounds represent superstructures of the α-ThSi(2) structure type through the long- and/or short-range vacancy ordering. RE(4)Ge(7) (RE = Pr, Nd, Sm) appear to be commensurately modulated 4-fold superstructure of REGe(2-x) (x = 1/4), while coexistence of commensurate and incommensurate modulation is revealed in the La- and Ce-analogues. These results shed more light on the structural evolution of the REGe(2-x) phases as function of the vacancy concentration and nature of the rare-earth metal. Measurements of the magnetic susceptibilities on well-characterized single-crystals show ferromagnetic, antiferromagnetic, and even spin-glass-like behaviors. Mean-field theory is used to evaluate the correlations between structural and magnetic property data. Measurements on the electrical resistivities and the heat capacities are also presented and discussed.

Magnesium substitutions in rare-earth metal germanides with the orthorhombic Gd5Si4-type structure. Synthesis, crystal chemistry, and magnetic properties of RE(5-x)Mg(x)Ge4 (RE = Gd-Tm, Lu, and Y).

A series of magnesium-substituted rare-earth metal germanides with a general formula RE(5-x)Mg(x)Ge(4) (x approximately = 1.0-2.3; RE = Gd-Tm, Lu, Y) have been synthesized by high-temperature reactions and structurally characterized by single-crystal X-ray diffraction. These compounds crystallize with the common Gd(5)Si(4) type structure in the orthorhombic space group Pnma (No. 62; Z = 4; Pearson's code oP36) and do not appear to undergo temperature-induced crystallographic phase transitions down to 120 K. Replacing rare-earth metal atoms with Mg, up to nearly 45% at., reduces the valence electron count and is clearly expressed in the subtle changes of the Ge-Ge and metal-metal bonding. Magnetization measurements as a function of the temperature and the applied field reveal complex magnetic structures at cryogenic temperatures and Curie-Weiss paramagnetic behavior at higher temperatures. The observed local moment magnetism is consistent with RE(3+) ground states in all cases. In the magnetically ordered phases, the magnetization cannot reach saturation in fields up to 50 kOe. The structural trends across the series and the variations of the magnetic properties as a function of the Mg content are also discussed.

Dynamics of photoexcited quasiparticles in heavy electron compounds.

Femtosecond real-time spectroscopy is an emerging new tool for studying low energy electronic structure in correlated electron systems. Motivated by recent advances in understanding the nature of relaxation phenomena in various correlated electron systems (superconductors, density wave systems) the technique has been applied to heavy electron compounds in comparison with their non-magnetic counterparts. While the dynamics in their non-magnetic analogues are similar to the dynamics observed in noble metals (only weak temperature dependences are observed) and can be treated with a simple two-temperature model, the photoexcited carrier dynamics in heavy electron systems show dramatic changes as a function of temperature and excitation level. In particular, below some characteristic temperature the relaxation rate starts to decrease, dropping by more than two orders of magnitude upon cooling down to liquid He temperatures. This behaviour has been consistently observed in various heavy fermion metals as well as Kondo insulators, and is believed to be quite general. In order to account for the experimental observations, two theoretical models have been proposed. The first treats the heavy electron systems as simple metals with very flat electron dispersion near the Fermi level. An electron-phonon thermalization scenario can account for the observed slowing down of the relaxation provided that there exists a mechanism for suppression of electron-phonon scattering when both the initial and final electronic states lie in the region of flat dispersion. An alternative scenario argues that the relaxation dynamics in heavy electron systems are governed by the Rothwarf-Taylor bottleneck, where the dynamics are governed by the presence of a narrow gap in the density of states near the Fermi level. The so-called hybridization gap results from hybridization between localized moments and the conduction electron background. Remarkable agreement with the model suggests that carrier relaxation in a broad class of heavy electron systems (both metals and insulators) is governed by the presence of a (weakly temperature dependent) indirect hybridization gap. Here we review the experimental results on a variety of heavy electron compounds, point out the common features as well as the peculiarities observed in some compounds, and compare the data with existing theoretical models.

High pressure effects on U L3 x-ray absorption in partial fluorescence yield mode and single crystal x-ray diffraction in the heavy fermion compound UCd11.

We report a study of high pressure x-ray absorption (XAS) performed in the partial fluorescence yield mode (PFY) at the U L3 edge (0­28.2 GPa) and single crystal x-ray diffraction (SXD) (0­20 GPa) on the UCd11 heavy fermion compound at room temperature. Under compression, the PFY-XAS results show that the white line is shifted by +4.1(3) eV at the highest applied pressure of 28.2 GPa indicating delocalization of the 5f electrons. The increase in full width at half maxima and decrease in relative amplitude of the white line with respect to the edge jump point towards 6d band broadening under high pressure. A bulk modulus of K0 = 62(1) GPa and its pressure derivative, K0 = 4.9(2) was determined from high pressure SXD results. Both the PFY-XAS and diffraction results do not show any sign of a structural phase transition in the applied pressure range.

Superconducting vortices in CeCoIn5: toward the Pauli-limiting field.

Many superconducting materials allow the penetration of magnetic fields in a mixed state in which the superfluid is threaded by a regular lattice of Abrikosov vortices, each carrying one quantum of magnetic flux. The phenomenological Ginzburg-Landau theory, based on the concept of characteristic length scales, has generally provided a good description of the Abrikosov vortex lattice state. We conducted neutron-scattering measurements of the vortex lattice form factor in the heavy-fermion superconductor cerium-cobalt-indium (CeCoIn5) and found that this form factor increases with increasing field-opposite to the expectations within the Abrikosov-Ginzburg-Landau paradigm. We propose that the anomalous field dependence of the form factor arises from Pauli paramagnetic effects around the vortex cores and from the proximity of the superconducting state to a quantum critical point.

Structure and properties of Gd3Ge4: the orthorhombic RE3Ge4 structures revisited (RE = Y, Tb-Tm).

The new binary compound Gd(3)Ge(4) has been synthesized and its structure has been determined from single-crystal X-ray diffraction. Gd(3)Ge(4) crystallizes in the orthorhombic space group Cmcm (No. 63) with unit cell parameters a = 4.0953(11) A, b = 10.735(3) A, c = 14.335(4) A, and Z = 4. Its structure can be described as corrugated layers of germanium atoms with gadolinium atoms enclosed between them. The bonding arrangement in Gd(3)Ge(4) can also be derived from that of the known compound GdGe (CrB type) through cleavage of the (infinity)(1)[Ge(2)] zigzag chains in GdGe and a subsequent insertion of an extra germanium atom between the resulting triangular fragments. Formally, these characteristics represent isotypism with the Er(3)Ge(4) type (Pearson's oC28). However, re-examination of the crystallography in the whole RE(3)Ge(4) series (RE = Y, Tb-Tm) revealed discrepancies and called into question the accuracy of the originally determined structures. This necessitated a new rationalization of the bonding, which is provided in the context of a comparative discussion concerning both the original and revised structure models, along with an analysis of the trends across the series. The temperature dependence of the magnetic susceptibility of Gd(3)Ge(4) shows that it is paramagnetic at room temperature and undergoes antiferromagnetic ordering below 29 K. Magnetization, resistivity, and calorimetry data for several other members of the RE(3)Ge(4) family are presented as well.

Photoexcited electron dynamics in Kondo insulators and heavy fermions.

We have studied the photoexcited carrier relaxation dynamics in the Kondo insulator SmB6 and the heavy fermion metal YbAgCu4 as a function of temperature and excitation level. The dynamic response is found to be both strongly temperature dependent and nonlinear. The data are analyzed with a Rothwarf-Taylor bottleneck model, where the dynamics are governed by the presence of a narrow gap in the density of states near the Fermi level. The remarkable agreement with the model suggests that carrier relaxation in a broad class of heavy electron systems (both metals and insulators) is governed by the presence of a (weakly temperature dependent) hybridization gap.

Vacancy ordering in SmGe2-x and GdGe2-x (x = 0.33): structure and properties of two Sm3Ge5 polymorphs and of Gd3Ge5.

The crystal structures and the magnetic properties of three new binary rare-earth intermetallic phases are reported. alpha-Sm3Ge5 and beta-Sm3Ge5 and Gd3Ge5 have been prepared from the corresponding elements through high-temperature reactions using the flux-growth method. The structures of the three compounds have been established using single-crystal X-ray diffraction: alpha-Sm3Ge5 crystallizes with its own type in the hexagonal space group P2c (No. 190) with cell parameters a = 6.9238(11) A, c = 8.491(3) A, and Z = 2, whereas beta-Sm3Ge5 adopts the face-centered orthorhombic Y3Ge5 type with space group Fdd2 (No. 43) and with cell parameters a = 5.8281(6) A, b = 17.476(2) A, c = 13.785(2) A, and Z = 8. The orthorhombic Gd3Ge5 with cell parameters a = 5.784(2) A, b = 17.355(6) A, and c = 13.785(5) A is isostructural with beta-Sm3Ge5. The structures of the title compounds can be described as AlB(2) and alpha-ThSi2 derivatives with long-range ordering of the germanium vacancies. Temperature-dependent DC magnetization (5-300 K) measurements show evidence of antiferromagnetic ordering below ca. 30 and 10 K for alpha-Sm3Ge5 and beta-Sm3Ge5, respectively. Gd3Ge5 undergoes two successive magnetic transitions below ca. 15 and 11 K. The temperature dependence of the resistivity and heat capacity of Gd3Ge5 are discussed as well.

Unusual Mn-Mn spin coupling in the polar intermetallic compounds CaMn2Sb2 and SrMn2Sb2.

Large single-crystals of two polar intermetallic phases, CaMn2Sb2 and SrMn2Sb2, have been grown using In or Sn as metal fluxes and characterized by single-crystal X-ray diffraction. The two compounds are isostructural and crystallize with the CaAl2Si2 structure (space group P3m1, No. 164) with unit cell parameters determined at 120(2) K of a = 4.5204(6) angstroms, c = 7.456(2) angstroms and a = 4.5802(17) angstroms, c = 7.730(5) angstroms for CaMn2Sb2 and SrMn2Sb2, respectively. Temperature- and field-dependent dc- and ac-magnetization measurements suggest complex magnetic ordering of the Mn moments below ca. 250 and 35 K for CaMn2Sb2 and below ca. 265 K for SrMn2Sb2. Resistivity measurements reveal metallic-like temperature dependence with rho(290) = 40 m omega cm for CaMn2Sb2 and rho290 = 100 m omega cm for SrMn2Sb2 with negligible magnetoresistance at 5 K in applied magnetic fields up to 10 kOe. Spin-polarized DFT electronic structure calculations confirm the metallic-like properties and provide further evidence for a magnetic structure where Mn atoms form two magnetic sublattices with ferromagnetic coupling within them and strong antiferromagnetic coupling between them.

Kondo scaling in the optical response of YbIn1-xAgxCu4.

Theoretical work on Kondo systems predicts universality in the scaling of observable quantities with the Kondo temperature, T(K). Here we report infrared-frequency optical response measurements of the correlated system YbIn(1-x)AgxCu4. We observe that x-dependent variations in the frequency and strength of a low-energy excitation are related to the x-dependent Kondo temperature. Comparison of the inferred trends with existing theory and a model calculation provides a framework in which to view these experimental results as scaling phenomena arising from local-moment/conduction electron hybridization.

Truly bulk-sensitive spectroscopic measurements of valence in heavy fermion materials.

Intermediate valence is one of the typical phenomena of systems with strong electronic correlation. The Anderson impurity model predicts a scaling of the valence with the reduced temperature T/T(K), which is difficult to observe by traditional surface-sensitive electronic spectroscopies. This paper presents results obtained by resonant inelastic X-ray scattering (RIXS), a bulk-sensitive configuration- and chemical-specific technique. The temperature dependence of the valence of YbInCu(4) and YbAgCu(4) was measured by tuning the incident energy to the resonance of the Yb(2+) spectral component. In the case of YbInCu(4) a sharp valence transition, as known from thermodynamical measurements, has been found. The valence of YbAgCu(4) reveals a smooth dependence consistent with a Kondo temperature T(K) = 70 K. These findings establish RIXS as a powerful tool for measuring bulk electronic properties of solids.

Probing the limits of the Zintl concept: structure and bonding in rare-earth and alkaline-earth zinc-antimonides Yb9Zn4+xSb9 and Ca9Zn4.5Sb9.

A new transition metal Zintl phase, Yb(9)Zn(4+x)Sb(9), was prepared by high-temperature flux syntheses as large single crystals, or by direct fusion of the corresponding elements in polycrystalline form. Its crystal structure was determined by single-crystal X-ray diffraction. Its Ca-counterpart, hitherto known as Ca(9)Zn(4)Sb(9), and the presence of nonstoichiometry in it were also studied. Yb(9)Zn(4+x)Sb(9) was found to exist in a narrow homogeneity range, as suggested from the crystallographic data at 90(3) K (orthorhombic, space group Pbam (No. 55), Z = 2): (1) a = 21.677(2) A, b = 12.3223(10) A, c = 4.5259(4) A, R1 = 3.09%, wR2 = 7.18% for Yb(9)Zn(4.23(2))Sb(9); (2) a = 21.706(2) A, b = 12.3381(13) A, c = 4.5297(5) A, R1 = 2.98%, wR2 = 5.63% for Yb(9)Zn(4.380(12))Sb(9); and (3) a = 21.700(2) A, b = 12.3400(9) A, c = 4.5339(4) A, R1 = 2.75%, wR2 = 5.65% for Yb(9)Zn(4.384(14))Sb(9). The isostructural Ca(9)Zn(4.478(8))Sb(9) has unit cell parameters a = 21.830(2) A, b = 12.4476(9) A, and c = 4.5414(3) A (R1 = 3.33%, wR2 = 5.83%). The structure type in which these compounds crystallize is related to the Ca(9)Mn(4)Bi(9) type, and can be considered an interstitially stabilized variant. Formal electron count suggests that the Yb or Ca cations are in the +2 oxidation state. This is supported by the virtually temperature-independent magnetization for Yb(9)Zn(4.5)Sb(9). Electrical resistivity data show that Yb(9)Zn(4.5)Sb(9) and Ca(9)Zn(4.5)Sb(9) are poor metals with room-temperature resistivity of 10.2 and 19.6 mOmega.cm, respectively.

Electrochemical and spectroscopic characterization of the novel charge-transfer ground state in diimine complexes of ytterbocene.

The novel charge-transfer ground state found in alpha,alpha'-diimine adducts of ytterbocene (C(5)Me(5))(2)Yb(L) [L = 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen)] in which an electron is spontaneously transferred from the f(14) metal center into the lowest unoccupied (pi*) molecular orbital (LUMO) of the diimine ligand to give an f(13)-L(*)(-) ground-state electronic configuration has been characterized by cyclic voltammetry, UV-vis-near-IR electronic absorption, and resonance Raman spectroscopies. The voltammetric data demonstrate that the diimine ligand LUMO is stabilized and the metal f orbital is destabilized by approximately 1.0 V each upon complexation for both bpy and phen adducts. The separation between the ligand-based oxidation wave (L(0/-)) and the metal-based reduction wave (Yb(3+/2+)) in the ytterbocene adducts is 0.79 V for both bpy and phen complexes. The UV-vis-near-IR absorption spectroscopic data for both the neutral adducts and the one-electron-oxidized complexes are consistent with those reported recently, but previously unreported bands in the near-IR have been recorded and assigned to ligand (pi*)-to-metal (f orbital) charge-transfer (LMCT) transitions. These optical electronic excited states are the converse of the ground-state charge-transfer process (e.g., f(13)-L(*-) <--> f(14)-L(0)). These new bands occur at approximately 5000 cm(-1) in both adducts, consistent with predictions from electrochemical data, and the spacings of the resolved vibronic bands in these transitions are consistent with the removal of an electron from the ligand pi* orbital. The unusually large intensity observed in the f --> f intraconfiguration transitions for the neutral phenanthroline adduct is discussed in terms of an intensity-borrowing mechanism involving the low-energy LMCT states. Raman vibrational data clearly reveal resonance enhancement for excitation into the low-lying pi* --> pi* ligand-localized excited states, and comparison of the vibrational energies with those reported for alkali-metal-reduced diimine ligands confirms that the ligands in the adducts are reduced radical anions. Differences in the resonance enhancement pattern for the modes in the bipyridine adduct with excitation into different pi* --> pi* levels illustrate the different nodal structures that exist in the various low-lying pi* orbitals.