Collapse of valence transition in Yb0.8Y0.2InCu4: pressure-induced weak ferromagnetism

We investigated the magnetization of Yb0.8Y0.2InCu4 as a function of temperature down to 0.6 K, pressure up to 1.2 GPa, and magnetic field up to 9 T. The valence transition temperature of Yb0.8Y0.2InCu4 is lowered with applying pressure. At 0.8 GPa, collapse of the valence transition and ferromagnetic ordering occur almost simultaneously. The ferromagnetic phase at 1.2 GPa is characterized by a low Curie temperature of 1.7 K and an extremely small ordered moment of 0.05 micro(B) per Yb. Some effect of screening the ordered moment may play a key role in the ferromagnetism and the valence transition.     

Band Jahn-Teller instability and formation of valence bond solid in a mixed-valent spinel oxide LiRh2O4

We have synthesized a new spinel oxide LiRh2O4 with a mixed-valent configuration of Rh3+ and Rh4+. At room temperature, it is a paramagnetic metal, but on cooling, a metal-insulator transition occurs and a valence bond solid state is formed below 170 K. We argue that the formation of valence bond solid is promoted by a band Jahn-Teller transition at 230 K and the resultant confinement of t_{2g} holes within the xy band. The band Jahn-Teller instability is also responsible for the observed enhanced thermoelectric power in the orbital-disordered phase above 230 K.     

Valence transition and magnetic ordering in Sn doped EuPd2Si2

The sharp, temperature induced, continuous valence transition in EuPd₂Si₂ is drastically changed by doping with Sn at the Si site upto 5 at. %. Only a first order valence transition occurs for a 3% Sn doped sample and the 2⁺ component which survives the valence transition orders magnetically at 4.2 K. No valence transition at all occurs for a 5% Sn doped sample right up to 1.9 K and magnetic ordering sets in around 30 K.     

Valence averaging and phase transitions in europium (Eu2VO4) and iron (RSr2Fe3O9) compounds

Mössbauer studies of ¹⁵¹Eu in Eu₂VO₄ reveal a very sharp valence averaging phase transition at 450 K. Two equally intense absorption lines, differing in isomer shift by 12.7 mm/s, corresponding to Eu²⁺ and Eu³⁺, collapse to a single absorption line at the average isomer shift. The transition is confirmed by X-ray and resistivity measurements. In RSr₂Fe₃O₉ (R=Pr, Sm) ⁵⁷Fe studies reveal averaging valence phase transitions coinciding with magnetic order phase transitions at 190 K and 140 K, respectively. Two magnetic sextets, corresponding to 2Fe³⁺ + Fe⁵⁺, collapse to two singlets corresponding to 2Fe⁴⁺ + Fe³⁺.     

Temperature induced valence instabilities in ternary Eu-pnictides: a comprehensive view

We report on measurements of the lattice constants, magnetic susceptibility, L_III X-ray absorption and Mössbauer-effect on EuNiP and EuPdP, which crystallize in the hexagonal layered Ni₂In structure. In both compounds the Eu valence above 510 K is 2.33. With decreasing temperature they show one (EuPdP) or two (EuNiP) first order phase transitions with a valence increase of about 0.16. At the same time thec-axis shrinks while the a-axis even increases. From Mössbauer measurements we show that the nature of the valence mixing is static. In contrast, the valence mixing in isostructural EuPtP is static at low temperatures, too, but it becomes homogeneous valent above a first order phase transition at 235 K. The behaviour of these compounds (as well as that of EuPdAs) is explained in a new model of electrostatically charged layers. In this model we can explain the temperature dependence of the lattice constants, the static valence mixing and the occurrence of preferred valences of the order 2 6/n. Together with the compression shift model of Hirst we can also understand the mechanism of the phase transitions. A comparison with EuT₂Si₂ compounds in ThCr₂Si₂ structure shows that in EuTX compounds only the electronic structure of the transition elements is relevant for the occurrence of mixed valency.     

Modeling of Nonthermal Solid‐to‐Solid Phase Transition in Diamond Irradiated with Femtosecond x‐ray FEL Pulse

In this contribution we review in detail our recently developed hybrid model able to trace simultaneously nonequilibrium electron kinetics, evolution of an electronic structure, and eventually nonthermal phase transition in solids irradiated with femtosecond free‐electron laser pulses. Diamond irradiated with an ultrashort intense x‐ray pulse serves as an example to show how an irradiated material undergoes an ultrafast phase transition on sub‐picosecond timescales. The transition of diamond into graphite is induced by an excitation of electrons from the valence band into the conduction band, which, in turn, induces a rapid change of the interatomic potential. Our theoretical model incorporates: a Monte‐Carlo method for tracing high‐energy electrons and K‐shell holes in diamond; a temperature equation for the valence‐band and low‐energy conduction‐band electrons; a tight binding method for calculation of the evolving electronic structure of the material and potential energy surfaces; and molecular dynamics propagating atomic trajectories. This unified approach predicts the damage threshold of diamond in a good agreement with experimentally measured values. It reveals a multi‐step nature of nonthermal phase transition being an interplay between electronic excitation, changes of the band structure, and atomic reordering. An effect of pulse parameters, such as photon energy and temporal pulse shape, on the phase transition is discussed in detail. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the nature of the valence transition in Eu(Pd1−xAux)2Si2

The intermediate valent compound series Eu(Pd_1−xAu_x)₂Si₂ has been studied by Mössbauer effect measurements on ¹⁵¹Eu(T = 4.2−300K) and ¹⁹⁷Au (4.2K) and by X-ray diffraction (10K, 300K). The temperature induced valence transition Eu²⁺ → Eu³⁺ for x < 0.175 is not of first order type, as suggested in a previous phase diagram [1]. The valence change of the Eu-ion is reflected also in the isomer shift of the ¹⁹⁷Au Mössbauer-resonance.     

Atomic approach to the mixed configuration ground state

A variational wave function proposed by Kaplan et al. is used to exhibit the mixed valence phenomena through f-d mixing interaction. The model is applied to the mixed valence samarium monochalcogenides and explains the pressure-induced phase transition.     

Entropy and phase diagram of valence transition

The electronic and lattice entropies associated with the valence transition are estimated. The electronic entropy in metallic phase is evaluated based on the model which includes the mixing between ?-level and d-band states, and the d-band superimposes the hybridized ?-level. The quasiharmonic approximation together with the Debye approximation are used to calculate the lattice entropy. For the first order transition occurring at low temperature the entropy of semiconducting phase is found to be lower than that of metallic phase. The reverse situation is obtained for high transition temperature. This explains the experimental fact that the slope of the phase boundary of valence transition in SmS changes its sign with temperature. The specific heat calculated in this model shows a broad maximum at low temperature.     

Competition between phase separation and "Classical" intermediate valence in an exactly solved model

The exact solution of the spin-1 / 2 Falicov-Kimball model on an infinite-coordination Bethe lattice is analyzed in the regime of "classical" intermediate valence. We find that (i) either phase separation or a direct metal-insulator transition precludes intermediate valence over a large portion of the phase diagram, and (ii) within the intermediate valence phase, only continuous transitions are found as functions of the localized f-electron energy or temperature.     

Electron spin resonance studies at the phase transition in YbInCu4

In the intermetallic compound YbInCu₄ the Gd³⁺-ESR and the static susceptibility were measured in the temperature range 1.5K–300 K, i.e. both below and above the valence phase transition which occurs in this material at T_ph≈50 K. The Gd³⁺ resonance is mainly determined by exchange interaction of Gd³⁺ ions with fluctuating Yb³⁺ ions via conduction electrons (RKKY coupling) both below and above this transition. Arguments are presented that at low temperature YbInCu₄ is a dense Kondo system (mixed valent state).     

Two dimensional ordering and fluctuations in alpha(')-NaV2O5

X-ray diffraction measurements of Bragg and diffuse scattering associated with charge ordering in the inorganic compound alpha(')- NaV2O5 show a continuous phase transition at a temperature of about 33.1 K. Many of this material's properties suggest a spin-Peierls transition, as established in CuGeO3 and MEM(TCNQ)(2). We compare the order parameter as well as fluctuations in the order parameter in these materials, and conclude that alpha(')- NaV2O5 is dissimilar, and that the transition is two dimensional in nature, due to charge ordering associated with the fractional average valence at the vanadium site within the orthorhombic a- b plane.     

Irreversible dynamics of the phase boundary in U(Ru0.96Rh0.04)2Si2 and implications for ordering

We report measurements and analysis of the specific heat and magnetocaloric effect-induced temperature changes at the phase boundary into the single magnetic field-induced phase (phase II) of U(Ru0.96Rh0.04)2Si2, which yield irreversible properties similar to those at the valence transition of Yb(1-x)Y(x)InCu4. To explain these similarities, we propose a bootstrap mechanism by which lattice parameter changes caused by an electric quadrupolar order parameter within phase II become coupled to the 5f-electron hybridization, giving rise to a valence change at the transition.     

X-ray Photoelectron Spectroscopy of Sb2S3 Crystals

The paper presents the X-ray photoelectron spectra (XPS) of the valence band and core levels of semiconductor ferroelectric Sb₂S₃ single crystals, which show weak phase transitions and anomalies of various physical properties. The XPS were measured with monochromatized Al K _α radiation in the energy range 0-1450 eV and the temperature range 160-450 K. The valence band is located 0.8-7.5 eV below the Fermi level. Experimental results of the valence band and core levels are compared with the results of theoretical ab initio calculations of the molecular model of Sb₂S₃ crystal. The chemical shifts in Sb₂S₃ crystal for the Sb and S states are obtained. Results revealed that the small structural rearrangements at the phase transition T _c1 = 300 K shift the Fermi level and all electronic spectrum. Also, temperature dependence of a spontaneous polarisation shifts the electronic spectra of the valence band and core levels. Specific temperature-dependent excitations in Sb 3d core levels are also revealed.     

Photoluminescence and photoluminescence excitation spectra of GaAs grown directly on Si

The photoluminescence of GaAs/Si grown by OMCVD has been analyzed as a function of temperature and the dominant high temperature line identified as a conduction-band-to-valence-band transition. Photoluminescence excitation spectra indicate that the transition is excitonic at 4.2 K. A second line, also identified as intrinsic, dominates the spectra below 100 K. A biaxial tensile strain is proposed to account for the two intrinsic lines through a splitting of the valence band degeneracy.     

Virtual levels,mixed valence phase and electronic phase transitions in rare earth compounds

We discuss the influence of the Coulomb interaction between localized and conduction electrons on the properties of magnetic impurities in metals and on electronic phase transitions such as the γ—α—α' transitions in Ce and the insulator—metal transition in SmS. Due to excitonic pairing between ?-holes and s-electrons, similar to that in excitonic insulators, the virtual ?-levels in metals may acquire an extra width, which, in contrast to the width in the Anderson model, depends upon the position of the ?-level, the width being the largest when the ?-level crosses the Fermi-level. This effect stabilizes the intermediate valence phase. As a result, in the Falicov model we get either a gradual phase transition (like that found in SmTe), or a first order one, followed by the intermediate valence phase (SmS), or, which is most interesting, two successive jump-like transitions with a mixed valence in between, similar to the γ—α—α' transitions in Ce. The mixed valence phase is described here as a kind of an “excitonic insulator”. The theory also predicts the correct slopes of the phase equilibrium lines for both Ce and SmS.     

Temperature-dependent structure and magnetization of YCrO3 compound

We have grown a YCrO$_3$ single crystal by the floating-zone method and studied its temperature-dependent crystalline structure and magnetization by x-ray powder diffraction and PPMS DynaCool measurements. All diffraction patterns were well indexed by an orthorhombic structure with space group of $Pbnm$ (No. 62). From 36 K to 300 K, no structural phase transition occurs in the pulverized YCrO$_3$ single crystal. The antiferromagnetic phase transition temperature was determined as $T_\textrm{N} = 141.58(5)$ K by the magnetization versus temperature measurements. We found weak ferromagnetic behavior in the magnetic hysteresis loops below $T_\textrm{N}$. Especially, we demonstrated that the antiferromagnetism and weak ferromagnetism appear simultaneously upon cooling. The lattice parameters ($a$, $b$, $c$, and $V$) deviate downward from the Grüneisen law, displaying an anisotropic magnetostriction effect. We extracted temperature variation of the local distortion parameter $\varDelta$. Compared to the $\varDelta$ value of Cr ions, Y, O1, and O2 ions show one order of magnitude larger $\varDelta$ values indicative of much stronger local lattice distortions. Moreover, the calculated bond valence states of Y and O2 ions have obvious subduction charges.     

Valence fluctuations in ternary europium compounds

We outline the possibility to study europium valence fluctuations with the μSR method and report on μSR experiments on the intermetallic compounds EuPdAs and NdPdAs. Above a magnetic transition at 15 K the temperature dependence of the relaxation rate in the trivalent neodymium system behaves like a typical localized moment system. In the valence fluctuating europium compound the zero field relaxation rate levels off at 1.0\ μs^-1 above 40 K. Furthermore, the relaxation enhancement in transverse field experiments is much smaller than expected for a pure dipolar coupling. Therefore an isotropic hyperfine coupling of typical strength is assumed and a valence fluctuation rate of 0.8 μs^-1 at 200 K is derived. Below the magnetic transition at 5 K a disordered spin freezing is concluded in EuPdAs. This revised version was published online in July 2006 with corrections to the Cover Date.     

XPS study of the phase transition in pure zirconium oxide nanocrystallites

Pure zirconium oxide nanocrystallites with diameters 6-140 nm are fabricated from ultrafine metallo-organic complexes by thermal hydrolysis at 120 °C and/or heat treatment at 125-1025 °C. X-ray photoelectron spectroscopy shows that effective ionic valence of Zr decreases with decreasing particle diameter. The size dependence of the ionic valences suggests that the phase transition from cubic to tetragonal occurs at an effective Zr valence of 2.0 near 3 nm in diameter and that the phase transition from tetragonal to monoclinic takes place at a critical size of 25 nm diameter with an effective Zr valence of about 2.6.