Itinerant and local magnetism,superconductivity and mixed valency phenomena in RM2Si2, (R = rare earth,M = Rh,Ru)°

X-Ray, magnetization and Mossbauer (¹⁵¹Eu, ¹⁵⁵Gd, ¹⁶¹Dy and dilute ⁵⁷Fe) studies of RM₂Si₂ reveal that when R is a magnetic ion the compounds order antiferromagnetically. For M = Rh a second antiferromagnetic phase transition is observed, corresponding to Rh itinerant electron magnetic ordering. In EuRh₂Si₂ the Eu ion is predominantly divalent with a mixed valent component. In EuRu₂Si₂ the Eu is predominantly trivalent. LaRu₂Si₂ and LuRu₂Si₂ display enhanced electron paramagnetism and become superconducting at 3.5 K and 2.4 K respectively. LaRh₂Si₂, YRh₂Si₂ and LuRh₂Si₂ display an itinerant electron magnetic phase transition, T_M (LaRh₂Si₂) = 7 K, and at lower temperatures a superconducting phase transition, T_c(LaRh₂Si₂) = 3.8 K. There is evidence that in the superconducting phase the itinerant magnetic order survives.     

Magnetic properties of R2Re2Si2C (R=Ho and Er)

We have investigated magnetic properties of R₂Re₂Si₂C (R=Ho and Er) using magnetic susceptibility, magnetization and heat capacity measurements. Both the materials order antiferromagnetically. The ordering temperatures (T_N) for Ho₂Re₂Si₂C and Er₂Re₂Si₂C are, ∼8.8 and ∼7.6 K, respectively. Our measurements indicate crystal field effects in the bulk properties of both these compounds. The experimental results have been analyzed by taking into account the effect of crystalline electric field and magnetic exchange interaction.     

Magnetic transitions in LaFe13−x−yCoySix compounds

The magnetic properties of a set of LaFe_13?x?yCo_ySi_x compounds (x = 1.6 ? 2.6; y = 0, y = 1.0) have been investigated using magnetic measurements, thermal expansion, ⁵⁷Fe Mössbauer spectroscopy and high resolution neutron powder diffraction methods over the temperature range 10–300 K. The natures of the magnetic transitions in these LaFe_13?x?yCo_ySi_x compounds have been determined. The Curie temperatures of LaFe_13?xSi_x were found to increase with Si content from T_C = 219(5) K for Si content x = 1.6 to T_C = 250(5) K for x = 2.6. Substitution of Co for Fe in LaFe_10.4Si_2.6 resulted in a further enhancement of the magnetic ordering temperature to T_C = 281(5) K for the LaFe_9.4CoSi_2.6 compound. The nature of the magnetic transition at the Curie temperature changes from first order for LaFe_11.4Si_1.6 to second order for LaFe_10.4Si_2.6 and LaFe_9.4CoSi_2.6. The temperature dependences of the mean magnetic hyperfine field values lead to T_C values in good agreement with analyses of the magnetic measurements. The magnetic entropy change, ?ΔS_M, has been determined from the magnetization curves as functions of temperature and magnetic field (ΔB = 0 ? 5 T) by applying the standard Maxwell relation. In the case of LaFe_12.4Si_1.6 for example, the magnetic entropy change around T_C is determined to be -ΔS_M ～ 14.5 J kg^?1 K^?1 for a magnetic field change Δ B = 0 ? 5 T.     

Local and itinerant Magnetism AND Crystal structure of RRh2Ge2 and RRu2Ge2 (r = rare earth)

The compounds RRh₂Ge₂; and RRu₂Ge₂ were synthesized X-ray studies show that they have the expected ThCr₂Si₂; tetragonal-type structure Magnetization studies at 1 8–300 K, ¹⁵¹Eu Mossbauer studies at 4 l, 77 and 300 K and the crystallography studies show the following- All RRh₂Ge₂; like RRh₂Si₂; exhibit two magnetic phase transitions, one corresponding to the antiferromagnetic ordering of the local rare earth moments. T_N = 8–90 K, the other corresponding to the itinerant electron ordering of the Rh sublattice. T_M = 3–9 K The heavy rare earths in RRu₂G₂; order antiferromagnetically and undergo a spin-flop transition in a relatively low magnetic field, <10 kOe The light elements in RRu₂Ge₂; order in a ferromagnetic, somewhat unclear structure NdRu₂Ge₂, like NdRu₂Si₂, exhibits two peaks in the magnetization curves Again, the lower may correspond to itinerant electron ordenng or, alternatively, to spin reorientation of the rare earth sublattice Eu in both EuRh₂Ge₂ and EuRu₂Ge₂ is divalent, whereas Ce in both CeRh₂Ge₂ and CeRu₂Ge₂ is trivalent For all rare earths the ordenng transition in RRh₂Ge₂ is higher than in RRu₂Ge₂. This fact can be associated with the smaller R-R distances in RRh₂Ge₂ and/ or due to the stronger magnetic character of the Rh 4d conduction electrons Companson of the magnetic properties and ¹⁵¹Eu hyperfine interactions of Eu²⁺Rh₂Ge₂, Eu²⁺Ru₂Ge₂, Eu²⁺Rh₂Si₂ and Eu³⁺Ru₂Si₂ with all the other systems leads to the conclusion that the conduction electrons play the dominant role in determining the magnetic properties of these systems Crystal-field effects are also of considerable importance, since the Mossbauer studies yield for the second-order crystal-field parameter A⁰₂〈r²_4f〉 the huge values +385 and +282 K for EuRu₂Ge₂; and EuRh₂Ge₂, respectively The easy axis of magnetization in the Eu compounds is in the basal plane The large second-order crystal field predicts well the direction of the easy axis for all other rare earths No superconductivity has been observed in any of the compounds, down to 1 8 K A companson of the magnetic properties of the germanides with those of the silicides shows great similanties, the differences being accounted for by the different unit cell sizes and c/a ratios.     

Implications of time-reversal symmetry for the band structure of single-wall carbon nanotubes

When electron states in carbon nanotubes are characterized by two-dimensional wave vectors with the components K ₁ and K ₂ along the nanotube circumference and cylindrical axis, respectively, then two such vectors symmetric about a M-point in the reciprocal space of graphene are shown to be related by the time-reversal operation. To each carbon nanotube there correspond five relevant M-points with the following coordinates: K ₁⁽¹⁾ = N/2R, K ₂⁽¹⁾= 0; K ₁⁽²⁾ = M/2R, K ₂⁽²⁾= −π/T; K ₁⁽³⁾= (2N −M)/2R, K ₂⁽³⁾= π/T; K ₁⁽⁴⁾= (M + N)/2R, K ₂⁽⁴⁾= -π/T, and K ₁⁽⁵⁾= (N − M)/2R, K ₂⁽⁵⁾= π/T, where M and N are the integers relating the chiral, C _h , symmetry, R, and translational, T, vectors of the nanotube by N R = C _h + M T, T = |T|, and R is the nanotube radius. The states at the edges of the one-dimensional Brillouin zone, which are symmetric about the M-points with K ₂ = ±π/T, are shown to be degenerate due to the time-reversal symmetry.     

Magnetic properties of ternary RMn2Si2 and RMn2Ge2 compounds

Magnetic properties of RMn₂Si₂ and RMn₂Ge₂ compounds, where R is a rare earth metal, have been investigated by magnetometric measurements. RMn₂Ge₂ (where R is a light rare earth) and LaMn₂Si₂ are ferromagnets. Remaining compounds have antiferromagnetic properties. DyMn₂Si₂ and ErMn₂Si₂ show ferromagnetic properties at low temperatures. It was confirmed that the value of Curie (or Néel) temperature for the Mn sublattice decreases with increasing c constant.     

First order magnetic phase transition in tetragonal NpCu2Si2

Magnetization and Np²³⁷ Mössbauer studies of the tetragonal compounds NpM₂Si₂ (M = Cr, Mn, Fe, Co, Ni, Cu) were performed. NpMn₂Si₂ is ferromagnetic. All other compounds order antiferromagnetically. Only in NpCu₂Si₂ the Mössbauer studies reveal a first order magnetic phase transition at T_N = 34 K. It is interpreted in terms of Blume's model, originally developed for cubic UO₂.     

Magnetic ordering in CeMnCuSi2

Temperature and field-dependent magnetization measurements on polycrystalline CeMnCuSi₂ reveal that the Mn moments in this compound exhibit ordering with a ferromagnetic (FM) component ordered instead of the previously reported purely antiferromagnetic (AFM) ordering. The FM ordering temperature, T_c, is about 120 K and almost unchanged with external fields up to 50 kOe. Furthermore, an AFM component (such as in a canted spin structure) is observed to be present in this phase, and its orientation is modified rapidly by the external magnetic field. The Ce L₃-edge X-ray absorption result shows that the Ce ions in this compound are nearly trivalent, very similar to that in the heavy fermion system CeCu₂Si₂. Large thermomagnetic irreversibility is observed between the zero-field-cooled (ZFC) and field-cooled (FC) M(T) curves below T_c indicating strong magnetocrystalline anisotropy in the ordered phase. At 5 K, a metamagnetic-type transition is observed to occur at a critical field of about 8 kOe, and this critical field decreases with increasing temperature. The FM ordering of the Mn moments in CeMnCuSi₂ is consistent with the value of the intralayer Mn–Mn distance R^a_Mn–Mn=2.890 Å, which is greater than the critical value 2.865 Å for FM ordering. Finally, a magnetic phase diagram is constructed for CeMnCuSi₂.     

Influence of Si and Co substitutions on magnetoelastic properties of R2Fe17 (R=Y, Er and Tm) intermetallic compounds

The magnetostriction of the off-stoichiometric R₂Fe₁₇-type intermetallic compounds based on R₂Fe_14−xCo_xSi₂ (R=Y, Er, Tm and x=0, 4) was measured, using the strain gauge method in the temperature range 77-460 K under applied magnetic fields up to 1.5 T. All compounds show sign change and reduction in magnetostriction values compared to the R₂Fe₁₇ compounds by Si substitution. For Y₂Fe₁₄Si₂ and Er₂Fe₁₄Si₂, saturation behaviour is observed near magnetic ordering temperature (T_C), whereas for Tm₂Fe₁₄Si₂, saturation starts from T>143 K. Also, Co substitution has different effects on the magnetostriction of R₂Fe₁₄Si₂ compounds. In Er₂Fe₁₀Co₄Si₂ and Tm₂Fe₁₀Co₄Si₂, saturation occurs below the spin reorientation temperature (T_SR). In addition, in Er₂Fe₁₄Si₂, a sign change occurs in the anisotropic magnetostriction (Δλ) as well as the volume magnetostriction (ΔV/V) at their T_SR values. The volume magnetostrictions of the Tm-containing compounds show an anomaly around their T_SR. In R₂Fe₁₄Si₂ compounds, parastrictive behaviour is also observed in ΔV/V near their T_C values. In addition, the magnetostriction of the sublattices is investigated. Results show that in R₂Fe₁₄Si₂ compounds, the rare-earth sublattice contribution to magnetostriction is negative and comparable to the iron sublattice, whereas, in R₂Fe₁₀Co₄Si₂ compounds, the rare-earth sublattice contribution is positive and larger than Fe sublattice. These results are discussed based on the effect of Si and Co substitutions on the anisotropy field of these compounds. Influence of the spin reorientation transition on the magnetostriction of these compounds is discussed in terms of the anisotropic sublattice interactions.     

Magnetism and hyperfine interactions in EuM2Ge2 and GdM2Ge2(M = Mn,Fe, Co,Ni, Cu)

X-ray, magnetic susceptibility and ¹⁵¹Eu, ¹⁵⁵Gd Mössbauer effect studies of EuM₂Ge₂ and GdM₂Ge₂ were performed. All compounds crystallize in the ThCr₂Si₂ body centered tetragonal structure. In all compounds, except those with M = Mn and in EuM₂Ge₂, the M component carries no magnetic moment. All compounds except those with Mn are antiferromagnetic at low temperatures. In EuMn₂Ge₂ the Mn moments order ferromagnetically at 330 K and change to antiferromagnetic order when the Eu moments order ferromagnetically (9 K). This behaviour is different from that in GdMn₂Ge₂, where the Mn sublattice orders antiferromagnetically at 365 K and becomes ferromagnetic and antiparallel to the ferromagnetic Gd sublattice at 96 K. The Mössbauer studies of ¹⁵¹Eu and ¹⁵¹Gd provide values for the magnetic hyperfine fields, the quadrupole interactions and the orientation of the magnetic moments relative to the local fourfold axis (c-axis). It turns out that in the Eu compounds the easy axis of magnetization is close to the c-axis, while in the Gd compounds it is in the basal plane. In all systems, excluding those with Mn, the interatomic rare earth-rare earth distances have the dominant effect on the conduction electron charge density and polarization at the rare earth site and on the Curie point.     

Magnetic properties of RM6Al6 (R = light rare earth,M = Cu,Mn, Fe)2

The systems RM₆Al₆ were studied by X-ray, magnetization and Mossbauer spectroscopy (⁵⁷Fe and ¹⁵¹Eu) measurements. The RCu₆Al₆ which crystallize in the f.c.c. NaZn₁₃ structure order ferromagnetically at low temperatures (T_c = 16KforR = Eu). The RMn₆Al₆ systems which crystallize in the rhombohedral Th₂Zn₁₇ structure order antiferromagnetically ($\text{T}{}_{\mathrm{<mtext>n</mtext>}}\text{= 25K for R = Nd}$and Eu). LaFe₆Al₆ has the NaZn₁₃ structure and orders antiferromagnetically at a relatively low temperature, 38K. The correlation of crystal structure and magnetic properties of these systems and those of RM₆Al₆ (R = heavy rare earth, tetragonal ThMn₁₂ structure) are discussed.     

Magnetic and57Fe Mössbauer studies of intermetallic compounds R2 (Fe1−x−y Ni x Co y )17 (R=Y,Gd,Tb,x=0,0.10, 0.20,y=0,0.05, 0.10)

Mössbauer studies of R₂(Fe_1?x?y Ni _x Co _y )₁₇ showed that the transferred hyperfine field at Fe nuclei due to magnetic rare earth (R) atoms is about one Tesla. Magnetic moments of the R atoms were determined from magnetic measurements as μTb=8.52μB, μGd=6.22μB. The mixed substitution of Ni and Co for Fe leads to an increase of the ordering temperature. A slight preference occupancy for Fe was observed involving the dumbbell shaped f or c site. The substitution effects of Ni and Co on the hyperfine field of f or c site, the average hyperfine field and the average isomer shift were also discussed.     

Magnetic properties and structural chemistry of ternary silicides (RE,Th, U)Ru2Si2 (RE = RARE EARTH)

Ternary silicides (RE, Th, U)Ru₂Si₂ have been synthesized from the elements. All the compounds (RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were found to be isotypic and to crystallize with the structure type of ThCr₂Si₂ (ordered derivative of the BaAl₄-type). The magnetic behavior of these alloys was studied in the temperature range 1.5 K < T < 1100 K. Magnetic susceptibilities at temperatures T > 300 K closely follow a typical Van Vleck paramagnetism of free RE³⁺-ions. In the case of CeRu₂Si₂ susceptibilities are well described for 20 K < T < 1100 K by a Van Vleck paramagnetism of widely spaced multiplets; the observed effective paramagnetic moment μ_eff = 2.12 BM indicates a high percentage (85%) of Ce³⁺. SmRu₂Si₂ yields an effective moment μ_eff = 0.54 BM, which compares reasonably well with the Hund's rule J = 5/2 ground level for free Sm⁺ and a low-lying excited level with J = 7/2. For temperatures T > 15 K the magnetic susceptibility as a function of temperature follows the “Van Vleck behavior” for free Sm³⁺. At low temperatures ferromagnetic ordering was encountered for (Pr, Nd, Ho, Er, Tm)Ru₂Si₂, whereas antiferromagnetic ordering was observed for (Sm, Gd, Tb, Dy)Ru₂Si₂. The ordering temperatures are generally below 55 K. No superconductivity was found for temperatures as low as 1.8 K.     

Magnetism and structural chemistry of ternary silicides: (RE,Th, U)Pt2Si2 (RE = rare earth)

Ternary silicides (RE, U, Th)Pt₂Si₂ have been prepared from the elements. All the compounds (RE= Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and U, Th) were found to be isotypic and crystallize with the primitive tetragonal CePt₂Si₂-type structure closely related to the CaBe₂Ge₂-type. The magnetic properties of these alloys were studied in the temperature range 1.5 K < T < 1100 K and in fields up to 1.3 T revealing a typical Van Vleck paramagnetism of free RE³⁺-ions for temperatures T > 200 K. A nonmagnetic ground state is reflected from the magnetic susceptibility data of CePt₂Si₂, which are interpreted in terms of interconfiguration fluctuations (ICF). The magnetic results of SmPt₂Si₂ (μ_eff = 0.7 BM) compare well with the ideal Van Vleck behavior of Sm₃₊ ions with a $\text{J =}\text{5}\text{2}$ ground state and a low-lying excited first level $\text{J =}\text{7}\text{2}$. At temperatures below 40 K antiferromagnetic ordering is found for (Gd, Tb, U)Pt₂Si₂; whereas in case of (Dy, Ho, Er, Tm)Pt₂Si₂ the onset of ferromagnetism is indicated below 4 K. None of the samples exhibited a superconducting transition above 1.8 K.     

Neutron diffraction study of the magnetic ordering in the series R 2 BaNiO 5 (R = Rare Earth)

A neutron diffraction study, as a function of temperature, of the title compounds is presented. The whole family (space group Immm, a ≈ 3.8?, b ≈ 5.8?, c ≈ 11.3?) is structurally characterised by the presence of flattened NiO₆ octahedra that form chains along the a-axis, giving rise to a strong Ni-O-Ni antiferromagnetic interaction. Whereas for Y-compound only strong 1D correlations exist above 1.5 K, presenting the Haldane gap characteristic of 1D AF chain with integer spin, 3D AF ordering is established simultaneously for both R and Ni sublattices at temperatures depending on the rare earth size and magnetic moment. The magnetic structures of R₂BaNiO₅ ( R = Nd, Tb, Dy, Ho, Er and Tm) have been determined and refined as a function of temperature. The whole family orders with a magnetic structure characterised by the temperature-independent propagation vector = (1/2, 0, 1/2). At 1.5 K the directions of the magnetic moments differ because of the different anisotropy of the rare earth ions. Except for Tm and Yb (which does not order above 1.5 K), the magnetic moment of the R³⁺ cations are close to the free-ion value. The magnetic moment of Ni²⁺ is around 1.4 , the strong reduction with respect to the free-ion value is probably due to a combination of low-dimensional quantum effects and covalency. The thermal evolution of the magnetic structures from T _N down to 1.5 K is studied in detail. A smooth re-orientation, governed by the magnetic anisotropy of R³⁺, seems to occur below and very close to T _N in some of these compounds: the Ni moment rotates from nearly parallel to the a-axis toward the c-axis following the R moments. We demonstrate that for setting up the 3D magnetic ordering the R-R exchange interactions cannot be neglected. Received 19 July 2001     

Magnetic ordering in NdRh2Si2 and ErRH2Si2

Neutron diffraction and magnetization study of polycrystalline NdRh₂Si₂ and ErRh₂Si₂ was performed in the temperature range from 4.2 to 293 K. Both compounds are of ThCr₂Si₂ type crystal structure and exhibit antiferromagnetic ordering below T_N = 53 K and T_N = 12.8 K respectively. The magnetic structure wave vector is τ = [0, 0, 1].     

Magnetic and hyperfine properties of NpFe2−xCoxSi2 tetragonal systems

Magnetization, ²³⁷Np Mössbauer effect and neutron diffraction studies of the tetragonal NpFe_2?xCo_xSi₂ (x = 0, 1, 1.5, 2) intermetallic compounds were performed. The Mössbauer studies of the²³⁷Np show a magnetic order below 87 (3)_, 15 (3), 37 (3), 42 (3) K, hyperfine fields of 2535 (50), 1600 (50), 2210 (50), 2600 (50) MHz and isometric shifts of -2.3 (3), +7.6 (3), 0 (3), -2.9 (3) mm/s (relative to NpAl₂), respectively. An extremely low magnetization of non-saturated character (at 4.2 K, 20 KOe) is observed.A polycrystalline ingot sample of NpCo₂Si₂ was studied by neutron diffraction at temperatures from 2 to 160 K. Five superlattice lines were observed at temperatures below 46 K and are consistent with an antiferromagnetic structure of the Np(2a) sublattice of type I with T_N = 46 (3) K. The Np ion magnetic moment consistent with the diffracted intensities is 1.5 (1) μ_B with no localized moment on the Co ion.A direct correlation between the Isomer shift, Hyperfine fields and ordering temperature is reported for the first time. This unusual correlation can be explained only if strong f-d, f-s hybridization are assumed.     

Magnetic phase transitions in Nd7Rh3 single crystal

Magnetic phase transitions in rare earth intermetallic compound Nd₇Rh₃ have been investigated using a single crystal. Measurement results of magnetization, magnetic susceptibility, specific heat, and electrical resistivity reveal that Nd₇Rh₃ has two magnetic phase transitions at T_N=34 K, T_t2=9.1 K and a change of the magnetic feature at T_t1=6.8 K in the absence of an external magnetic field. Antiferromagnetic orderings exist in all the three magnetic states; a large magnetic anisotropy between the c-axis and the c-plane is observed. In the magnetic phase below T_t2, an irreversible field-induced magnetic phase transition takes place in the c-plane; after removing external magnetic field, a coexistence state of ferro- and antiferromagnetic ordering or a ferrimagnetic state having a remanent magnetization M_R is stabilized. The M_R decays to a certain value for several hours after the first process; a magnetic field cooling effect was also observed in the c-plane below T_t2. In the antiferromagentic state above T_t2, the irreversibility disappears and an ordinary antiferromagnetic state takes place. As the origin of this phenomenon, a kind of martensitic structural transition that is observed in Gd₅Ge₄ can be considered.     

Molecular field theory analysis of R2Fe17C (R=PR,Nd, Gd,Tb, Dy,Ho, Er)

The temperature dependence of magnetization is analysed for R₂Fe₁₇C via the two-sublattice molecular field theory. The molecular field coefficients n_FF, n_RF and n_RR are obtained, by which T_C was calculated. Using the least-squares method, the fitted-form of H_R(T) varying with temperature for each compound is presented. The results are analysed. In addition, the parameters F=M_Fe²(0)n_FF/T_C was calculated for each R₂Fe₁₇C. By F, some phenomena different from the normal view were explained.     

Superconductivity and magnetic order in RBa2Cu3Oz

Mössbauer studies of⁵⁷Fe in RBa_2?y K _y (Cu_1?x Fe _x )₃O_z, with R=Y and Pr;y=0 and 0.5;x=0.01, 0.05 and 0.1 andz between 5.9 and 7.1, have been performed. A minority of the iron ions enter the Cu(2) site and reveal its magnetic order. In nonsuperconducting YBa_1.5K_0.5(Cu_0.95Fe_0.05)₃O_6.1 two distinctly inequivalent magnetic iron sites are observed, probably corresponding to iron in the Cu(2) site with different Ba?K neighbours. In superconducting (T _c =60 K) YBa_1.5K_0.5(Cu_0.95Fe_0.05)₃O_6.5 one Cu(2) subsite remains magnetic (T _N=440 K). The implications of these findings on the valencies of the Cu ions are discussed.