We have demonstrated that the middle-infrared (mid-IR) peaks in the optical conductivity spectra of Ce$X_3$ ($X$ = Pd, Sn, In) can be explained by first-principle band structure calculation with the spin-orbit interaction. The mid-IR peak shapes in these materials are not identical to one another: CePd$_3$, CeSn$_3$, and CeIn$_3$ have a triple-peak structure, double-peak structure and broad single-peak structure, respectively. These peaks can be theoretically explained by the optical transition from the occupied state to the spin-orbit splitted Ce $4f$ state. This result indicates that the mid-IR peaks originate from the simple band picture with the Ce $4f$ state near the Fermi level, not from the conventional cf hybridization gap based on the periodic Anderson model.
The importance of taking into account inter-site $f-f$ hybridization in electron structure calculations for Ce metal and cerium heavy fermion compounds was studied. We demonstrate that for heavy-fermion systems such as cerium compound CeCu$_2$Si$_2$ $f-f$ 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 combini…
The thermodynamic Bethe ansatz equations for the N = 6 Coqblin-Schrieffer model with crystal fields have been solved numerically. The realistic case of three Kramers doublets with arbitrary splittings has been studied for the first time. The specific heat has been calculated for representative combinations of the ionic energy splittings providing ample material for comparison with experimental results for Cerium impurities and compounds.
We propose a new framework for first-principle calculations of heavy-fermion materials. These are described in terms of the Kondo lattice Hamiltonian with the parameters extracted from a realistic density functional based calculation which is then solved using continuous-time quantum Monte Carlo method and dynamical mean field theory. As an example, we show our results for the Neel temperatures of Cerium-122 compounds (CeX2Si2 with X=Ru, Rh, Pd, Cu, Ag, and Au) where the general trend around the magnetic quantum critical point is successfully reproduced. Our results are organized on a universa…
The properties of the novel heavy fermion superconductor Ce$_3$PtIn$_{11}$ are investigated by thermodynamic and transport measurements at ambient and under hydrostatic pressure. At ambient pressure the compound exhibits two successive magnetic transitions at $T_1$ $\approx$ 2.2 K and $T_{\rm N}$ $\approx$ 2 K into antiferromagnetically ordered states and enters into a heavy fermion superconducting phase below $T_{\rm c}$ $\approx$ 0.32 K. The coexistence of long-range magnetic order and superconductivity is discussed in the context of the existence of the two crystallographically inequivalent…
The study of competing ground states is a central issue in condensed matter physic. In this article we will discuss the interplay of antiferromagnetic order and unconventional superconductivity in Ce based heavy-fermion compounds. In all discussed examples superconductivity appears at the border of magnetic order. Special focus is given on the pressure-temperature-magnetic field phase diagram of CeRhIn5 and CeCoIn5 which allows to discuss microscopic coexistence of magnetic order and superconductivity in detail. A striking point is the similarity of the phase diagram of different classes of st…
Cerium (Ce)-based heavy-fermion materials have a characteristic double-peak structure (mid-IR peak) in the optical conductivity [$σ(ω)$] spectra originating from the strong conduction ($c$)--$f$ electron hybridization. To clarify the behavior of the mid-IR peak at a low $c$-$f$ hybridization strength, we compared the $σ(ω)$ spectra of the isostructural antiferromagnetic and heavy-fermion Ce compounds with the calculated unoccupied density of states and the spectra obtained from the impurity Anderson model. With decreasing $c$-$f$ hybridization intensity, the mid-IR peak shifts to the low-energ…
The low-temperature behavior of Ce2RuZn4 has been investigated. Specific heat and magnetic susceptibility data reveal an antiferromagnetic transition at a Neel temperature of 2 K. Ce2RuZn4 is a static intermediate-valent compound with two crystallographically independent cerium atoms. The magnetic data clearly show that only one cerium site is magnetic (Ce^3+), while the second one carries no magnetic moment. The experimental data are interpreted with the help of first principles electronic structure calculations using density functional theory and the augmented spherical wave method. The calc…
In an effort to explore the differences between rare-earth-based and uranium-based heavy Fermion (HF) compounds that reflect the underlying difference between local 4$f$ moments and itinerant 5$f$ moments we analyze scaling laws that relate the low temperature neutron spectra of the primary ("Kondo-esque") spin fluctuation to the specific heat and susceptibility. While the scaling appears to work very well for the rare earth intermediate valence compounds, for a number of key uranium compounds the scaling laws fail badly. There are two main reasons for this failure. First, the presence of anti…
Among the Cerium compounds, the heavier monochalcogenides CeY (Y=S,Se,Te) of cerium provide a class of compounds which together with the heavier monopnictides CeX (X=N,P,As,Sb,Bi) exhibit extremely interesting physical properties. The hybridization of the partially delocalized f-electrons seems to be responsible for the unusual properties, in particular the magnetic ones which show great chemical sensitivity. As compared to the monopnictides, the monochalcogenides have an additional anion p-electron which shifts the Fermi energy into the p-region of the Cerium 5d-derived density of states, and…
This comment clarifies the mixed definition of the cerium valence in the article entitled: Quantitative study of the $f$ occupation in CeMIn5 and other cerium compounds with hard X-rays, published in Journal of Electron Spectroscopy and Related Phenomena http://www.sciencedirect.com/science/article/pii/S0368204816300123 and available on arXiv:1601.03270. Indeed, it is unclear wether electrons belonging on hybridized f-states are part or not of the valence. When one tries to simulate the system, an Anderson impurity model only includes valence bands electrons and localized 4-f states. Therefore…
The Doniach's diagram has been originally proposed to describe the competition between the local Kondo effect and the intersite RKKY interactions in cerium compounds. Here we discuss the extension of this diagram to different variations of Kondo lattice model. We consider a) ordered cerium compounds where the competition between magnetic order and Kondo effect plays an important role, as $CeRh_2Si_2$, b) disordered cerium systems with competing spin glass phase, magnetic ordered phases and a Kondo phase, as the heavy fermion cerium alloy $CeCu_xNi_{1-x}$ and, c) uranium compounds where a coexi…
We present bulk-sensitive hard x-ray photoelectron spectroscopy (HAXPES) data of the Ce3d core levels and lifetime-reduced L edge x-ray absorption spectroscopy (XAS) in the partial fluorescence yield (PFY) mode of the CeMIn5 family with M = Co, Rh, and Ir. The HAXPES data are analyzed quantitatively with a combination of full multiplet and configuration interaction model which allows correcting for the strong plasmons in the CeMIn5 HAXPES data, and reliable weights wn of the different fn contributions in the ground state are determined. The CeMIn5 results are compared to HAXPES data of other h…
The electronic structures of cerium-based ternary 122 compounds Ce$M_{2}$Si$_{2}$, where $M =$ Ru, Rh, Pd, and Ag, are investigated systematically by using the density functional theory in combination with the single-site dynamical mean-field theory. The momentum-resolved spectral functions, total and 4$f$ partial density of states, self-energy functions, and valence state fluctuations are calculated. The obtained results are in good accord with the available experimental data. It is suggested that, upon increasing atomic number from Ru to Ag, the 4$f$ electrons should become increasingly loca…
In order to unveil the 4f electronic structures in cerium monopnictides (CeX, where X = N, P, As, Sb, and Bi), we employed a state-of-the-art first-principles many-body approach, namely the density functional theory in combination with the single-site dynamical mean-field theory, to make detailed calculations. We find that the 4f electrons in CeN are highly itinerant and mixed-valence, showing a prominent quasi-particle peak near the Fermi level. On the contrary, they become well localized and display weak valence fluctuation in CeBi. It means that a 4f itinerant-localized crossover could emer…
We present a non-linear elastic model of a coherent transition with discontinuous volume change in an isotropic solid. The model reproduces the anomalous thermodynamics typical of coherent equilibrium including intrinsic hysteresis (for a pressure driven experiment) and a negative bulk modulus. The novelty of the model is that the statistical mechanics solution can be easily worked out. We find that coherency leads to an infinite-range density--density interaction, which drives classical critical behavior. The pressure width of the hysteresis loop shrinks with increasing temperature, ending at…
We have applied the bond valence method to cerium oxides to determine the oxidation states of the Ce ion at the various site symmetries of the crystals. The crystals studied include cerium dioxide and the two sesquioxides along with some selected intermediate phases which are crystallographically well characterized. Our results indicate that cerium dioxide has a mixed-valence ground state with an f-electron population on the Ce site of 0.27 while both the A- and C-sesquioxides have a nearly pure f^1 configuration. The Ce sites in most of the intermediate oxides have non-integral valences. Furt…
R2RhIn8 compounds (space group P4/mmm, R is a rare-earth element) belong to a large group of structurally related tetragonal materials which involves several heavy-fermion superconductors based on Ce. We have succeeded to grow single crystals of compounds with Nd, Dy and Er and following our previous bulk measurements, we performed neutron-diffraction studies to determine their magnetic structures. The Laue diffraction experiment showed that the antiferromagnetic order below the Néel temperature is in all three compounds characterized by the propagation vector k = (1/2, 1/2, 1/2). The amplitud…
The competition between spin glass, ferromagnetism and Kondo effect is analysed here in a Kondo lattice model with an inter-site random coupling $J_{ij}$ between the localized magnetic moments given by a generalization of the Mattis model which represents an interpolation between ferromagnetism and a highly disordered spin glass. Functional integral techniques with Grassmann fields have been used to obtain the partition function. The static approximation and the replica symmetric ansatz have also been used. The solution of the problem is presented as a phase diagram giving $T/{J}$ {\it versus}…
The crystal-field splittings of the monopnictides and monochalcogenides of Cerium (CeX and CeY) and their alloys (CeX$_{1-x}$Y$_x$) are calculated by means of an \emph{ab initio} many-body combined technique. The hybridization functions of the 4f states of Cerium with the conduction band for each material are obtained from first principles within the local density approximation (LDA) and are used as input for the Anderson impurity model, which is solved within a multi-orbital Non-Crossing Approximation (NCA). This realistic theoretical approach (LDA-NCA) is able to reproduce the experimental r…
Cerium hexaboride is a cubic f-electron heavy-fermion compound that displays a rich array of low-temperature magnetic ordering phenomena which have been the subject of investigation for more than 50 years. Its complex behaviour is the result of competing interactions, with both itinerant and local electrons playing important roles. Investigating this material has proven to be a substantial challenge, in particular because of the appearance of a "magnetically hidden order" phase, which remained elusive to neutron-scattering investigations for many years. It was not until the development of mode…
The cerium alpha-gamma phase transition is characterized by means of a many-body Jastrow-correlated wave function, which minimizes the variational energy of the first-principles scalar-relativistic Hamiltonian, and includes correlation effects in a non-perturbative way. Our variational ansatz accurately reproduces the structural properties of the two phases, and proves that even at temperature $T=0$K the system undergoes a first order transition, with ab initio parameters which are seamlessly connected to the ones measured by experiment at finite $T$. We show that the transition is related to …
Single-crystalline CeRh3Si2 was investigated by means of x-ray diffraction, magnetic susceptibility, magnetization, electrical resistivity, and specific heat measurements carried out in wide temperature and magnetic field ranges. Moreover, the electronic structure of the compound was studied at room temperature by cerium core-level x-ray photoemission spectroscopy (XPS). The physical properties were analyzed in terms of crystalline electric field and compared with results of ab-initio band structure calculations performed within the density functional theory approach. The compound was found to…
The electronic properties of Cerium (Ce) and ytterbium (Yb) intermetallic compounds may display a more local or more itinerant character depending on the interplay of the exchange interactions among the $4f$ electrons and the Kondo coupling between $4f$ and conduction electrons. For the more itinerant case, the materials form heavy-fermions once the Kondo effect is developed at low temperatures. Hence, a temperature variation occurs in the electronic structure that can be traced by investigating the optical conductivity ($σ(ω)$) spectra. Remarkably, the temperature variation in the $σ(ω)$ spec…
We have calculated optical conductivity [$σ(ω)$] spectra of ytterbium compounds (YbAl$_3$, YbAl$_2$, YbCu$_2$Si$_2$, YbNi$_2$Ge$_2$, YbInCu$_4$, YbRh$_2$Si$_2$, YbIr$_2$Si$_2$, and YbB$_{12}$) based on the direct interband transition derived from first-principle band calculation and compared the results with the experimentally obtained $σ(ω)$ spectra. The spectral feature of a peak in the middle-infrared region (mid-IR peak) and a shoulder structure in the far-infrared region (far-IR shoulder) in the experimental $σ(ω)$ spectra can be described by the band calculation with a common renormaliza…
We report an extensive study on the intrinsic bulk electronic structure of the high-temperature superconductor CeFeAsO0.89F0.11 and its parent compound CeFeAsO by soft and hard x-ray photoemission, x-ray absorption and soft-x-ray emission spectroscopies. The complementary surface/bulk probing depth, and the elemental and chemical sensitivity of these techniques allows resolving the intrinsic electronic structure of each element and correlating it with the local structure, which has been probed by extended-x-ray absorption fine structure spectroscopy. The measurements indicate a predominant 4f1…
We present theoretical results for a Kondo-lattice model with spin-1/2 localized moments, including both the intrasite Kondo coupling and an intersite antiferromagnetic exchange interaction, treated within an extended mean-field approximation. We describe here the case of a non-integer conduction-band filling for which an ``exhaustion'' problem arises when the number of conduction electrons is not large enough to screen all the lattice spins. This is best seen in the computed magnetic susceptibility. The Kondo temperature so obtained is different from the single-impurity one, and increases for…
Ytterbium-based delafossites with effective S=1/2 moments are investigated intensively as candidates for quantum spin-liquid ground states. While the synthesis of related cerium compounds has also been reported,many important details concerning their crystal, electronic, and magnetic structures are unclear. Here we analyze the S=1/2 system KCeO2, combining complementary theoretical methods. The lattice geometry was optimized and the band structure investigated using density functional theory extended to the level of a GGA+U calculation in order to reproduce the correct insulating behavior. The…
We present a detailed investigation of the hole (3\% Re) doping effect on the polycrystalline CeRu$_{2}$Al$_{10}$ sample by magnetization, heat capacity, resistivity, muon spin rotation ($μ$SR), and neutron scattering (both elastic and inelastic) measurements. CeRu$_2$Al$_{10}$ is an exceptional cerium compound with an unusually high Neel temperature of 27 K. Here we study the stability of the unusual magnetic order by means of controlled doping, and we uncover further surprising attributes of this phase transition. The heat capacity, resistivity and $μ$SR measurements reveal an onset of magne…
Cu2OSeO3 is known as a unique example of insulating multiferroic compounds with skyrmion spin texture, which is characterized by the chiral cubic crystal structure at ambient pressure. Recently, it has been reported that this compound shows pressure-induced structural transition with large enhancement of magnetic ordering temperature Tc. In the present study, we have investigated the detailed crystal structure in the high pressure phase, by combining the synchrotron X-ray diffraction experiment with the diamond anvil cell and the analysis based on the genetic algorithm. Our results suggest tha…
Crystal and magnetic structures of a series of novel quantum spin trimer system Ca3Cu3xNix(PO4)4 (x=0,1,2) were studied by neutron powder diffraction at the temperatures 1.5-290 K. The composition with one Ni per trimer (x=1) has a monoclinic structure (space group P 21 /a, no. 14) with the unit cell parameters a = 17.71 A, b = 4.89 A, c = 8.85 A and = 123.84 deg at T=290 K. The (x=2) composition crystallizes in the C 2/c space group (no. 15) with the doubled unit cell along c-axis. Each trimer is formed by two crystallographic positions: one in the middle and the second one at the ends of the…
The caged compound LaRu2Zn20 exhibits a structural transition at TS =150 K, whose driving mechanism remains elusive. We have investigated atomic dynamics by the measurements of specific heat C and inelastic X-ray scattering (IXS). The lattice part of the specific heat Clat divided by T3, Clat/T3, shows a broad peak at around 15 K, which is reproduced by two Einstein modes with characteristic temperatures of 35 K and 82 K, respectively. IXS measurements along the [111] and [110] directions reveal optical phonon modes at 3 meV (35 K) and 7 meV (80 K), respectively, whose values agree with the va…
Frustrated magnetic compounds, in particular low-dimensional, are topical research due to persistent uncover of novel nontrivial quantum states and potential applications. The problem of this field is that many important results are scattered over the localized parameter ranges, while areas in between still contain hidden interesting effects. We consider $J_1-J_2-J_3$ Heisenberg model on the square lattice and use the spherically symmetric self-consistent approach for spin-spin Green's functions in "quasielastic" approximation. We have found a new local order in spin liquids: antiferromagnetic…
