Thermodynamic properties of the CeSn3 mixed valence compound

We have measured on the CeSn₃ compound, the expansion coefficient between 80 and 800 K at normal pressure, the isothermal compressibility in the 0–8 GPa pressure range at room temperature and the heat capacity at constant pressure in the 60–300 K temperature range. The experimental data were compared with those previously found for the isomorphous LaSn₃ phase, assumed as a proper reference material for the study of the intermediate valency states in CeSn₃. Both the thermal expansion (3α) and the isothermal compressibility (k) of CeSn₃ show behaviours quite different from those of LaSn₃: for instance, in the standard conditions, 3α is 55 × 10^?6K^?1for CeSn₃ and 38 × 10^?6K^?1for LaSn₃; k is 15 × 10^?12 Pa^?1 and 12 × 10^?12 Pa^?1 respectively for CeSn₃ and LaSn₃. The thermal behaviour of the molar specific heat at constant pressure of CeSn₃ is similar to that of LaSn₃ for temperatures lower than 50 K. In the 70–300 K temperature range, the heat capacity of CeSn₃ is clearly higher than that of LaSn₃, ΔC_p being maximum near 150 K. The analysis of the calorimetric data show that the electronic coefficient γ of CeSn₃ is temperature dependent: its value varies from 53 mJ K^?2 mole^?1 at low temperature 24 mJ K^?2 mole^?1 at 300 K.     

Search for phonon anomalies in the intermediate valence compound CeSn3

The phonon dispersion relations of the intermediate valence compound CeSn₃ and the integral valence reference compound LaSn₃ were measured by inelastic neutron scattering. They are quite similar and no phonon anomalies due to valence fluctuations in CeSn₃ were detected. Likewise no line broadening was observed. Model calculations revealed, that the influence of the “breathing” deformability of the rare earth ions on the lattice dynamics is only moderate; moreover the breathing force constant turned out to be equal for both CeSn₃ and LaSn₃.     

Finite temperature lattice softening in CeSn3

Results of temperature dependent Mossbauer effect measurements on Sn in CeSn₃ and LaSn₃ are presented. An anomalous increase in the Sn mean squared displacement (MSD) in CeSn₃ in the 50K region surrounding 135K has been observed. A phenomological model is developed which relates the results to previous measurements on CeSn₃. This model discusses lattice softening effects near continuous, isomorphic phase transitions such as occur in a number of rare earth compounds.     

Thermodynamic and magnetic properties of LaSn3

Thermal expansion coefficient between 77 and 900K, isothermal compressibility in the 0–80 Kbar pressure range, magnetic susceptibility between 77 and 1300 K and heat capacity at constant pressure in the 20–300 K temperature range were determined for the LaSn₃ compound. From the experimental data, the specific heat at constant volume was calculated and the thermal dependence of the Debye's parameter θ_D was obtained. The electron contribution to the heat capacity was also determined from the high temperature data. The magnetic properties confirm that there is no evidence of the existence of a magnetic moment localized on La atoms, in contrast with a previous report and in agreement with the general assumptions. A little anomaly found in the expansion coefficient, in the isothermal compressibility and in the specific heat is discussed in terms of a lattice order-disorder phenomenon.     

Ultrasonic attenuation in pure and Gd-Doped superconductors: LaSn3 and LaAl2

We have investigated the ultrasonic attenuation (UA) in the pure and magnetically doped superconductors LaSn₃ and LaAl₂, the latter being an ideal Abrikosov-Gorkov system. The UA of pure LaSn₃ and LaAl₂ agrees well with BCS prediction. The experiments in doped LaSn₃ proved difficult due to high background attenuation. The results in La_1?nGd_nAl₂ (_n = 0.377 at .%), though, show a significant discrepancy with the theories which is not understood.     

Phonon anomalies in mixed valent CeSn3

Inelastic neutron scattering techniques have been used to measure the phonon dispersion curves of CeSn₃ and LaSn₃. Close to the zone boundary in the [111] symmetry direction pronounced differences were observed between the measured phonon frequencies of these two compounds.     

Anomalous Tc-behavior of LaSn3 under pressure

The superconducting transition temperature T_c of LaSn₃ has been measured up to ～ 22 kbar and was observed to increase through a maximum under hydrostatic compression. The anomalous T_c-behavior is attributed to a pressure induced Fermi surface topology change.     

Induced neutron magnetic form factor of LaSn3

Polarized neutron scattering techniques have been used to study the spatial distribution of the magnetization induced in a single crystal of LaSn₃ by a magnetic field of 42.5 kG at 100 K. We find that the magnetic form factor decreases very rapidly with increasing scattering angle, and bears no resemblance to the spin or orbital free-atom magnetic form factor. The experimental results are in reasonable agreement with band theoretical calculations of the spin magnetic form factor of LaSn₃. We conclude that (a) the spin part is the dominant contribution to the bulk susceptibility of LaSn₃ and (b) there is a substantial amount of Sn-5p electronic character in the wavefunctions near the Fermi level.     

Anomalous magnetic behaviour and susceptibility maximum in CeSn3

Anomalous magnetic behaviour observed in one of cerium intermetallic compound, CeSn₃, is analysed in the spirit of the Fermi liquid model, by regarding even the 4f-electrons of cerium as itinerant. It is shown that the appearance of the broad peak of the susceptibility at about 150°K can be attributed to the T²1nT dependence of the susceptibility on temperature.     

稀土金属间化合物CeSn3和CeIn3的能带理论

本文报道了CeSn₃和CeIn₃的能带计算结果。对其f电子的行为,以及f电子与非f原子的s,p,d电子之间的杂化进行了讨论。分析了费密能级附近的态密度分布及能带结构。 关键词：     

Magnetic structure of the compound CeIn3

Neutron diffraction measurements on the CeIn₃ compound show that the magnetic ordered phase is an antiferromagnetic one with a propagation vector ($\text{1}\text{2}$, $\text{1}\text{2}$, $\text{1}\text{2}$) and a weak value of the magnetic moment 0.48±0.08 μ_B. Comparison are made with the CeAl₂ and CeSn₃ cases.     

Mode softening and the elastic constants of CeSn3

The transverse and longitudinal acoustic velocities have been measured in the [100] and [111] directions of CeSn₃ as a function of temperature for 4.2 ≤ T ≤ 290 K. The elastic constants c₄₄ and $\text{1}\text{2}\text{(c}{}_{11}\text{?c}{}_{12}\text{)}$ increase smoothly with decreasing temperature and become temperature independent below 10 K but the bulk modulus has a 2% decrease at 135 K which is indicative of an electronically driven mode softening.     

Pressure induced phonon frequency shifts in mixed valent CeSn3

Pressure induced phonon frequency shifts have been determined in mixed valent CeSn₃. The results evaluated as mode Grüneisen parameters show rather normal positive values. There is no conclusive evidence for a pressure induced enhancement of the mixed valent character of this material.     

Upper critical fields of superconducting Gd and Tm doped LaSn3: Effects of crystalline electric fields

The temperature dependence of the upper critical fields, H_c²(T), are presented for (La_1-xGd_x)Sn₃ and (La_1-xTm_x)Sn₃. For samples with nearly the same T_c, H_c²(T) of the Tm-doped LaSn₃ samples are always larger than those for the Gd-doped samples. The results are interpreted in terms of crystalline electric field splitting of magnetic levels of the Tm³⁺. Pure LaSn₃ is found to be a Type I superconductor.     

Heat capacity of EuMnO3 and Eu0.7A0.3MnO3 (A=Ca,Sr) compounds

We carried out the heat capacity calculation of the magnetoresistance compounds EuMnO₃ and Eu_0.7A_0.3MnO₃ (where A=Ca and Sr) as a function of temperature from 5 to 100 K, using the Rigid Ion Model (RIM). The results on heat capacity for EuMnO₃ and Eu_0.7A_0.3MnO₃ (A=Ca and Sr) obtained by us are in good agreement with the measured values. Although strong electron–phonon interactions are present in these compounds but the lattice part of the specific heat also deserves proper attention. The parent compound EuMnO₃ exhibits two magnetic transitions at 35 and 47 K due to weak ferromagnetic (FM) component and antiferromagnetic (AF) ordering. In addition, we have reported cohesive energy (φ), molecular force constant (f), compressibility (β), Restrahalen frequency (υ₀), Debye temperature (θ_D) and Gruneisen parameter (γ) in the temperature range 5 K?T?100 K.     

Specific heat and magnetic susceptibility of MnF2 and Mn0.98Fe0.02F2 near TN

The antiferro- to paramagnetic phase transition of the weakly anisotropic compound MnF₂ has been studied by means of heat capacity, magnetic susceptibility and thermal expansion measurements. The critical-point parameters associated with the specific heat indicate a transition according to the theoretical Ising-model. The temperature derivative of the parallel magnetic susceptibility times temperature (d(χ∥T)/dT) and the c-axis thermal expansion coefficient show a critical behaviour very similar to that of the specific heat. The influence of iron doping on the critical behaviour has been investigated by studies on Mn_0.98Fe_0.02F₂. Specific heat and magnetic susceptibility measurements show an unexpectedly sharp transition although some rounding off is noticed as compared to pure MnF₂.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

The heat capacity of the layer compound tetrachlorobis (methylammonium) manganese—II (CH3NH3)2MnCl4, from 10 to 300k

The heat capacity of the layer compound, tetrachlorobis (methylammonium) manganese II, (CH₃NH₃)₂MnCl₄, has been measured over the range 10K <T<300K. In this region, two structural phase transitions have been observed previously by other techniques: one transition is from a monoclinic low temperature (MLT) phase to a tetragonal low temperature (TLT) phase, and the other is from TLT to an orthorhombic room temperature (ORT) phase. The present experiments have shown that the lower transition (MLT→TLT) occurs at T = 94.37±0.05K with ΔH_t = 727±5 J mol^?1 and ΔS_t = 7.76±0.05 J K^?1 mol^?1, and the upper transition (TLT→ORT) takes place at T = 257.02±0.07K with ΔH_t = 116±1J mol^?1 and ΔS_t = 0.451±0.004 J K^?1mol^?1. These results are discussed in the light of recent measurements on (CH₃NH₃)₂CdCl₄, and also with regard to a recent theoretical model of the structural phase transitions in compounds of this type.In addition to the structural phase transitions, (CH₃NH₃)₂MnCl₄ also undergoes magnetic ordering at T < 150K. The magnetic component to the heat capacity, as deduced from a corresponding states comparison of the heat capacity of the present compound with that of the Cd compound, is shown to be consistent with the behaviour expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Nature of optical properties of GdFe3(BO3)4 and GdFe2.1Ga0.9(BO3)4 crystals and other 3d5 antiferromagnets

Influence of the partial substitution of paramagnetic Fe³⁺ ions by diamagnetic Ga³⁺ ions in the trigonal crystal GdFe₃ (BO₃)₄ on its optical and magnetic properties is studied and discussed in connection with problems common for all antiferromagnets containing 3d ⁵ ions. Polarized optical absorption spectra and linear birefringence of GdFe₃ (BO₃)₄ and GdFe_2.1Ga_0.9 (BO₃)₄ single crystals have been measured in the temperature range 85–293 K. Specific heat temperature dependence (2–300 K) and structure of GdFe_2.1Ga_0.9 (BO₃)₄ crystal have been also studied. As a result of substitution of 30% Fe to Ga the Neel temperature diminishes from 38 till 16 K, the strong absorption band edge shifts on 860 cm^-1 (0.11 eV) to higher energy and the d-d transitions intensity decreases substantially larger than the Fe concentration does. Strong absorption band edge is shown to be due to Mott-Hubbard transitions. Correlation between position of the strong absorption band edge and the Neel temperature of antiferromagnets has been revealed. Properties of the doubly forbidden d-d transitions in the studied crystals and in other antiferromagnets are explained within the framework of the model of the exchange-vibronic pair absorption, which is theoretically analyzed in detail. The model permitted us to determine the connection between parameters of d-d absorption bands (intensity, width and their temperature dependences), on the one hand, and the exchange, spin-orbit and electron-lattice interactions, on the other hand.