Thermodynamic scaling theory for the two-impurity Anderson model

We present results of a study of the two-impurity Anderson model using a thermodynamic scaling theory developed recently. The model is characterized by the Coulomb energy U, the orbital energy epsilond, the d-level width Gamma, and the separation between impurities R. If Gamma<<−epsilond<fluctuating valence'' with the singlet lying lower in energy, i.e., epsilond>~Gamma. Here we find that the single-impurity physics dominates the low-temperature behavior, and impurity-impurity interactions are perturbative. The qualitative features of the temperature-dependent susceptibility are discussed. Journal of Applied Physics is copyrighted by The American Institute of Physics.

Effect of hole localization on Madelung potential of YBa2Cu3O7

The Madelung potential and formation energy of the superconducting compound YBa2Cu3O7 have been computed for hole localization at different sites in the crystal. The cases considered include Cu3+ ion at Cu(1) and Cu(2) sites, O− ion at O(1), O(2), O(3) and O(4) sites and combinations of O− and Cu3+ ions at O(4) and Cu(1) and O(2,3) and Cu(2) sites. The two lowest-energy configurations correspond to Cu3+ ion at Cu(1) site and O− ion at O(4) site. The difference in formation energy between those configurations is relatively small. The next preferred configuration corresponds to simultaneous partial localization of the hole at Cu (1) site and O(1) site. Other configurations are much less stable. The results suggest a resonating or fluctuating valence model for YBa2Cu3O7.

He II spectra of La, Ce and Yb: Novel features in the valence band region

He II photoelectron spectra of La, Ce and Yb show features which cannot be explained in terms of single electron excitations. It is proposed that these are due to formation of electron-hole paris.

Theory For The Anomalous Hall Constant Of Mixed-Valence Systems

We show that the large anomalous Hall constants of mixed-valence and Kondo-lattice systems can be understood in terms of a simple resonant-level Fermi-liquid model. Splitting of a narrow, orbitally unquenched, spin-orbit split, f resonance in a magnetic field leads to strong skew scattering of band electrons. We interpret both the anomalous signs and the strong temperature dependence of Hall mobilities in CeCu2Si2, SmB6, and CePd3 in terms of this theory.

3d and 4d core level X-ray photoelectron spectroscopy of mixed-valence CePd3

3d and 4d core-level XPS spectra for CePd3, a mixed-valence system, have been measured. Each spectrum exhibits two sets of structures, each corresponding to one of the valence states of cerium. Thus the usefulness of XPS, which has so far not been used extensively to investigate the mixed-valence cerium systems, is pointed out.

Valence bond analysis of the Kondo chain Hamiltonian

Accurate extrapolations for the ground state energy per site of the one - dimensional Kondo chain system is obtained from exact finite system calculations carried out employing a valence bond scheme. An analysis of the ground state wave function indicates that the localized spin is quenched for all nonzero values of the Kondo exchange constant in one dimension.

Valence fluctuation in some Yb intermetallics by X-ray photoemission and X-ray absorption

The valence state of Yb in some of its intermetallics, YbNi2Ge2, YbCu2Si2 and YbPd2Si2 has been investigated by LIII(Yb) absorption edges and X-ray pnotoelectron spectra in the 4f and 4d regions. These studies establish the presence of mixed valence in all three systems and illustrate the utility of 4f and 4d spectra in the study of mixed valence in Yb compounds.

Valence states and magnetic properties of LaNi1-xMnxO3 (for 0≤x≤0.2 and x=0.5)

Single-phase LaNi1-xMnxO3 samples in the compositional range 0valence states at room temperature for x=0.1, 0.2 and 0.5. Magnetic susceptibility data suggest Mn4+ solute ions and Stoner-enhanced Pauli paramagnetism of the metallic solvent for x=0.01 with a smooth transition to Mn3+ solute ions and a spontaneously magnetised solvent conduction band at x=0.05. Below 200K, the x=0.05 sample forms superparamagnetic clusters, and below 40K there is evidence for an antiferromagnet spin-density wave. Comparisons with LaCo0.95Mn0.05O3 and La0.98Sr0.02CoO3 confirm that the long-range magnetic coupling occurs via solvent electrons in a narrow conduction band. The conductivity changes from that of a narrow-band metal for x<0.01 to that more characteristic of diffusive motion for x>0.05, but any motional enthalpy appears to remain small ( Delta Hm approximately=0). The x=0.1 sample exhibits ferrimagnetic spin glass behaviour below 40K, and the ferromagnetic interactions increase with manganese concentration. The oxide with x=0.50 is ferromagnetic with a well defined Curie temperature.

On the valence state of molybdenum in Ce2MoO6

he valence state of molybdenum in cubic Ce2MoO6 was investigated using magnetic susceptibility measurements, electron spin resonance spectroscopy and X-ray absorption spectroscopy. The results are consistent with the formulation Ce3+Ce4+Mo5+O6.

On the valence state of molybdenum in Ce2MoO6

The valence state of molybdenum in cubic Ce2MoO6 was investigated using magnetic susceptibility measurements, electron spin resonance spectroscopy and X-ray absorption spectroscopy. The results are consistent with the formulation Ce3+Ce4+Mo5+O6.

X-ray absorption spectroscopic study of the mixed valence system CePd3

Mixed valency in CePd3 has been examined by a study of the LIII (Ce) absorption edge in this compound as well as other model compounds. In CePd3, peaks characteristic of 3+ and 4+ states of Ce are found to be separated by 2 eV.

High-pressure magnetic susceptibility of the intermediate valence system EuPd2Si2

The pressure dependence (0-7 kbar) of the magnetic susceptibility is reported for the intermediate valence system EuPd2Si2 in the temperature interval 77-300K. It is found that the thermally induced valence transition becomes more gradual on application of pressure The characteristic fluctuation temperature Tf, also seems to be pressure dependent.

Family of Mixed-Valence Oxovanadium(IV/V) Dinuclear Entities Incorporating N4O3-Coordinating Heptadentate Ligands: Synthesis, Structure, and EPR Spectra

Dinuclear ((VVV)-V-IV) oxophenoxovanadates of general formula [V2O3L] have been synthesized in excellent yields by reacting bis(acetylacetonato)oxovanadium(IV) with H3L in a 2:1 ratio in acetone under an N-2 atmosphere. Here L3- is the deprotonated form of 2,6-bis[{{(2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L1), 2,6-bis[{{(5-methyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L2) 2,6-bis[ {{(5-tert-butyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenoI (H3L3), 2,6-bis[{{(5-chloro-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L4) , 2,6-bis[{{(5-bromo-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L5), or 2,6-bis[{{(5-methoxy-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L6). In [V2O3L1], both the metal atoms have distorted octahedral geometry. The relative disposition of two terminal V=O groups in the complex is essentially cis. The O=V...V=O torsion angle is 24.6(2)degrees. The V-O-oxo-V and V-O-phenoxo-V angles are 117.5(4) and 93.4(3)degrees, respectively. The V...V bond distance is 3.173(5) Angstrom. X-ray crystallography, IR, UV-vis, and H-1 and V-51 NMR measurements show that the mixed-valence complexes contain two indistinguishable vanadium atoms (type 111). The thermal ellipsoids of O2, O4, C10, C14, and C15 also suggests a type III complex in the solid state. EPR spectra of solid complexes at 77 K display a single line indicating the localization of the odd electron (3d(xy)(1)). Valence localization at 77 K is also consistent with the V-51 hyperfine structure of the axial EPR spectra (3d(xy)(1) ground state) of the complexes in frozen (77 K) dichloromethane solution: S = 1/2, g(parallel to) similar to 1.94, g(perpendicular to) similar to 1.98, A(parallel to) similar to 166 x 10(-4) cm(-1), and A(perpendicular to) similar to 68 x 10(-4) cm(-1). In contrast isotropic room-temperature solution spectra of the family have 15 hyperfine lines (g(iso) similar to 1.974 and A(iso) similar to 50 x 10(-4) cm(-1)) revealing that the unpaired electron is delocalized between the metal centers. Crystal data for the [V2O3L1].CH2Cl2 complex are as follows: chemical formula, C32H43O6N4C12V2; crystal system, monoclinic; space group, C2/c; a = 18.461(4), b = 17.230(3), c = 13.700(3) Angstrom; beta = 117.88(3)degrees; Z = 8.

Spatial survival probability for one-dimensional fluctuating interfaces in the steady state

We report numerical and analytic results for the spatial survival probability for fluctuating one-dimensional interfaces with Edwards-Wilkinson or Kardar-Parisi-Zhang dynamics in the steady state. Our numerical results are obtained from analysis of steady-state profiles generated by integrating a spatially discretized form of the Edwards-Wilkinson equation to long times. We show that the survival probability exhibits scaling behavior in its dependence on the system size and the "sampling interval" used in the measurement for both "steady-state" and "finite" initial conditions. Analytic results for the scaling functions are obtained from a path-integral treatment of a formulation of the problem in terms of one-dimensional Brownian motion. A "deterministic approximation" is used to obtain closed-form expressions for survival probabilities from the formally exact analytic treatment. The resulting approximate analytic results provide a fairly good description of the numerical data.

Evidence for double valence fluctuation in metallic oxides of lead

The possible role of double valence fluctuation in both lead and oxide ions with reference to metallization in oxides of lead is examined by x-ray-photoemission spectroscopy, ultraviolet-photoemission spectroscopy (UPS), and 207Pb NMR studies. The double valence fluctuations may be viewed as Pb4++2O2-⇄Pb2+O22-. While the insulating oxides PbO, Pb3O4, and Sr2PbO4 show a single oxide ion, O2- characterized by O(1s) at 529.7 eV, the insulating peroxide BaO2 is characterized by the ion O22- with a single O(1s) at 533 eV. The metallic PbO2, BaPbO3, BaBiPbO3, and SrPbO3 showed the occurrence of both O2- and O22- ions. The valence band in these compounds has also been studied by UPS, and clear evidence for the coexistence of O2- and O22- is seen in PbO2. A simultaneous study of 207Pb NMR suggests that the Pb ion could also exist in mixed-valence states. Qualitative arguments are presented to rationalize the existence of such mixed valences of the anion in metal oxides in general and their role in superconductivity.