Raman scattering in intermediate valent SmB6

We have measured the Raman spectra of intermediate valent (IV) SmB₆ and compared it to LaB₆ and EuB₆. Beside the three high energy Raman active phonons we found additional features in the spectra. Most prominent is a peak at 172 cm^-1 for SmB₆, at 214 cm^-1 for LaB₆ and at ～220 cm^-1 for EuB₆. The spectra are analysed in terms of defect induced phonon excitations yielding a weighted phonon density of states. The softening of the line in IV SmB₆ compared to the other hexaborides is unusual since even in the trivalent MB₆ compounds the Raman active phonon modes normally are at lower frequencies than in semiconducting, divalent samples. This phonon softening is explained in analogy with the phonon anomalies in other IV compounds like Sm_1?xY_xS and TmSe.     

Point-contact spectroscopy on SmB6, TmSe,LaB6 and LaSe

We measured the dynamic resistance dU/dI (U) and its derivative d²U/dI²(U) of point contacts with intermediate valent SmB⁶ and TmSe and their integer valent reference compounds LaB₆ and LaSe at liquid helium temperatures. While dU/dI(U) for point contacts with LaB₆ and LaSe did not show any anomalous structures, for SmB₆ and TmSe a strong resistance peak at zero voltage was observed with a characteristic width of ～ 5 mV for SmB₆ and ～ 2.5 mV for TmSe.     

Optic phonon anomalies and f-d hybridization in SmS and SmB6

The optic phonons of semiconducting SmS and of (homogeneously) mixed-valent SmS and SmB₆ have been investigated by means of Raman scattering. The dominant electron - phonon interaction upon resonantly exciting the 4f shell is revealed as a coupling of the strongly localized 4f hole at the Sm site to full symmetric (A_{j g}) displacements of the nearest neighbour anions i.e. mainly to LO(L) phonons. Semiconducting and mixed-valent, metallic SmS show a “softening” of the LO(L) phonon frequencies with respect to the other divalent and trivalent rare earth sulfides, respectively, going in parallel with a “softening” of the bulk modulus. The f-d hybridization is considered as the common origin of these phonon frequency renormalizations.     

ESCA study of electronic structure of SmB6

The electronic structure of SmB₆ was investigated by X-ray photoelectron spectroscopy (XPS or ESCA). The spectrum of each core level of Sm in SmB₆ consists of three peaks. Such a splitting was not observed in Sm₂O₃, SmF₃, and SmB₄. The analysis of the results shows that three kinds of Sm ions — Sm²⁺(4f⁶), Sm²⁺(4f⁵5d^0.86s^0.2), and another Sm²⁺ — are present in SmB₆. The last kind of Sm ions is probably localized in a surface region.     

Study of the valence transition in La- and Yb-substituted SmB6

Lattice parameter and magnetic susceptibility measurements have been made on Sm_1?xLa_xB₆ and Sm_1?yYb_yB₆ alloys. The results indicate that La³⁺ substitution for Sm in SmB₆ decreases the Sm valence, whereas substitution with Yb²⁺ increases the Sm valence. It is found that the contribution of Sm³⁺ to the susceptibility disappears for a wide range of composition.     

Nuclear spin relaxation,hybridization, and low-temperature 4f spin fluctuations in intermediate-valent SmB6

¹¹B spin-lattice relaxation measurements have been carried out in SmB₆ samples with large low-temperature resistivities. Above 15 K the relaxation is activated, with approximately the same gap (≈6 meV) as found previously in transport and optical measurements. 4f spin fluctuations apparently dominate the relaxation, so that these results give strong evidence for 4f-conduction band hybridization at the gap edge. An anomalous peak in the relaxation rate was observed at ≈5 K, which is tentatively attributed to fluctuations of “remagnetized” Sm³⁺ ions near Sm-site vacancies.     

Azimuthal anisotropy in low-energy ion scattering from SmB6 (001)

A remarkable azimuthal anisotropy has been observed in the scattering of He⁺ ions of an incident energy of 1 KeV from the SmB₆(001) surface. The anisotropy can be interpreted on the basis of “shadowing” effects and clearly reflects the structure of the surface.     

Pulsed magnetic field study of the spin gap in intermediate valence compound SmB6

In this work, we report the behavior of electrical resistivity of SmB₆ at temperatures between 2.2 and 70 K in pulsed magnetic fields up to 54 T. A strong negative magnetoresistance was detected with increasing magnetic field, when lowering the temperature in the range T<30 K. We show that the amplitude of negative magnetoresistance reaches its maximum dR/R~70% at B=54 T, in the vicinity of phase transition occurring in this strongly correlated electron system at T_C~5 K. The crossover from negative magnetoresistance to positive magnetoresistance found at intermediate temperatures at T>30 K is discussed within the framework of exciton-polaron model of local charge fluctuations in SmB₆ proposed by Kikoin and Mishchenko. It seems that these exciton-polaron in-gap states are influenced both by temperature and magnetic field.     

Destruction of the gap in the intermediate valence compound SmB6 by neutron irradiation

The electrical resistivity ? of a SmB₆ single crystal has been measured during and after a fast neutron irradiation performed at 21 K : for the first time, it is shown that a very low defect concentration destroys the low temperature divergence of ? in this compound. These results are considered as an evidence of the existence of an intrinsic gap in pure SmB₆, and of its destruction by point defects. On the contrary, the irradiation has increased the resistivity value at 300 K, confirming the metallic character of SmB₆ at this temperature. The recovery of defects at 300 K is very weak.     

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.     

Evidence for p-f mixing in U3P4 and U3As4 from optical spectroscopy

The near normal incidence reflectivity of the ferromagnets U₃P₄ and U₃As₄ and the isostructural but diamagnetic compounds Th₃P₄ and Th₃As₄ has been measured from 0.03 to 12 eV. Trithorium tetraphosphide and tetraarsenide are shown to be indirect gap semiconductors with gap energies of 0.43 and 0.39 eV, respectively. U₃P₄ and U₃As₄ display similar sets of p→d transitions than the corresponding thorium compounds, however, they are shifted by 0.85 eV to lower photon energies. It is concluded that the uranium compounds are metals due to a merging of the valence p band into the 6d conduction band giving direct experimental evidence for a p-f mixing effect of the same size. Energy level schemes are derived.     

Self- and foreign-gas-broadened lineshapes in the ν1 band of NH3

Precise N₂, O₂, H₂, Ar, He, and self-broadenings and shifts have been obtained for Q- and R-branch transitions in the ν₁ fundamental band of ammonia from simultaneous fits of low-noise, high-resolution difference-frequency laser spectra at pressures from 0.07 to 27 kPa (0.5-200 Torr). Observed lineshapes exhibit significant deviations from the conventional Voigt profile, which may be attributed to Dicke narrowing and/or speed-dependent broadening. At the higher pressures, line mixing is evident and must be included in the fits. For self-broadening, line mixing is dominated by collisional tunneling transitions, whereas for the non-polar buffers, rotational relaxation among selected K states is the primary mixing mechanism.     

Two-dimensional critical behaviour in antiferrodistortive Al ur6(CIO4)3 and Ga ur6(ClO4)3

Critical behaviour with dimensionality d = 2 has been observed for the 300 K antiferrodistortive phase transition in Al ur₆(ClO₄)₃ and Ga ur₆(ClO₄)₃ by means of the temperature dependence of the ESR parameter D. The systems exhibited d = 2 behaviour in the static critical behaviour for T<T_c?40 K for T>T_c + 40 K. From the ESR data including line width measurements the local order parameter relaxation rate ω₁ has been obtained for various temperatures above T_c, with a lowest value of ω₁ = 150 MHz at T_c + 15 K     

Predictions of multiphoton resonances in SF6 and SiF4

The frequency dependence of the multiphoton resonances to the rotation-vibrational levels of the first two ν₃ overtones are calculated for SF₆ and SiF₄. From these calculations we can identify most of the features seen in the high intensity SF₆ absorption data and predict those features that would be seen in similar SiF₄ data.     

Photoelectron spectra of As4S3, P4S3, P4Se3 and As4O6

The He(I) UV photoelectron spectra of As₄S₃, P₄S₃, P₄Se₃ and As₄O₆ are reported in this paper. The spectra of As₄S₃ and the isostructural molecules P₄S₃ and P₄Se₃ comprise seven broad but clearly defined peaks, whilst the spectrum of As₄O₆ consists of six peaks and two shoulders. By comparing the spectra with one another and with the photoelectron spectra of other arsenic and phosphorus compounds, the character and symmetry species of the highest-energy occupied molecular orbitals of the molecules have been assigned.     

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.     

Spectroscopic and magnetic properties of Fe3Fe4(AsO4)6

The infrared (IR) and ⁵⁷Fe-Mössbauer spectra of Fe₃^IIFe₄^III(AsO₄)₆ were recorded and analyzed on the basis of its structural characteristics. The IR spectrum presents a high complexity, showing an important number of bands and splittings, as a consequence of the presence of three structurally independent AsO₄³⁻ groups. The analysis of the four quadrupole signals shown by the Mössbauer spectrum allowed to attain a detailed insight into the cation distribution over the available crystallographic sites. The alternating current susceptibility measurements indicate a paramagnetic to ferrimagnetic transition in the material at about 59 K.     

Electron spin resonance investigation of the structural phase transitions in Alurea6(ClO4)3 and Ga urea6(ClO4)3

Second order structural phase transitions in Alur₆(ClO₄)₃ and Gaur₆(ClO₄)₃ with T_c ～ 300 K are studied by means of ESR on single crystals doped with the analogous Cr(III) compound. The transitions are antiferrodistortive and of the displacive type, the displacements resulting from the condensation of a X₂ mode $\text{(k = (0}\text{1}\text{2}\text{1}\text{2}\text{))}$ of the ClO₄ ions. The ESR parameters have the same temperature dependence as the order parameters and can be described by D and E～φ～. The space group describing the structure changes from S₆² to S₂¹, and the number of domains is multiplied by three. Above 300 K the crystals already consist of two domains, resulting from a ferrodistortive phase transition D_3d⁶ → S₆². The actual transition temperature of the latter phase transition lies at some temperature above the decomposition temperature of the crystals.     

Domain-like magnetic structure in superconductors of ErRh4B4 and HoMo6S8 type

The problem of the coexistence of superconductivity and magnetic order is studied by taking into account the indirect exchange interaction, magnetic dipolar interaction and magnetic anisotropy. It is shown that the domain-like magnetic structure should be realized in the superconducting phases of ErRh₄B₄ and HoMo₆S₈ at the temperatures T_m = 1.4 and 0.7 K respectively. The transition from superconducting domain-like phase (DS) to the normal ferromagnetic (FN) state is described.     

Degenarate four-wave mixing in LiNbO3 and LiTaO3

Continuous wave generation of complex conjugate wavefront via four-wave mixing in LiNbO₃ and LiTaO₃ with diffusion non-linearity is studied. Strong anisotropy of the degenarate four-wave mixing is observed and explained.