Nuclear hyperfine effects in Dy(OH)3

A crystal field analysis of the experimental data on magnetic, optical and thermal properties of Dy(OH)₃ single crystals have been published The nuclear hyperfine properties of Dy³⁺ in Dy(OH)₃ were studied using a crystal field thus obtained. The hyperfine spectra were computed from 4–20 K with a minimum number of approximations. Under a weak crystal field, the lowest electronic level is a Kramers' doublet For this highly anisotropic crystal, the magnetic hyperfine and the quadrupole interactions are both prominent The quadrupole interaction energy is temperature dependent The value of the magnetic Sternheimer factor R_hf/R is determined to be 0 14 The observed specific heat $\text{C}{}_{\mathrm{hf}}\text{R}$ arising from hyperfine interactions have been explained satisfactorily A maxima is expected at 21 mK.     

Heat capacity of a five-coordinated ferromagnet,chloro bis(N,N-diethyldithiocarbamato)iron(III), in the temperature range from 0.4 to 20 K

The heat capacity of polycrystalline Fe[S₂CN(C₂H₅)₂]₂Cl has been measured in the temperature range from 0.411 to 19.55 K. The transition between ferromagnetic and paramagnetic states is characterized by a sharp λ-type anomaly centered at the Curie temperature, T_c = 2.412 ± 0.008 K. The enthalpy and the entropy of transition are 40.475 J mol^?1 and 11.199 J K^?1mol^?1 (= 1.347 R), respectively. The transition entropy is only 2.81% smaller than R In 4. This fact ascertains that the spin manifold is really a quartet. The ground spin states of the present compound are characterized by a zero-field splitting of the $\text{S =}\text{3}\text{2}$ state into two Kramers' doublets. The overlapping non-cooperative Schottky-type anomaly due to the energy separation between the two Kramers' doublets is separated tentatively from the cooperative heat capacity due to the exchange interaction. Based on a careful analysis of the transition entropy it may be concluded that the magnetic structure of the present complex would be a two-dimensional triangular Ising lattice. The exchange and the Curie-Weiss constants are also determined to be 0.155 and 4.19 K, respectively.     

Dependence on interatomic distance of exchange coupling in rare-earth Al2 compounds

The effect of pressure on the Curie temperature of the heavy rare-earth dialuminides has been measured up to 3.5 kbar. The derivatives dT_c/d_p are 0.00(4), 0.09, 0.21, 0.39, 0.60 and 0.71 K/kbar respectively for TmAl₂ ErAl₂, HoAl₂, DyAl₂, TbAl₂ and GdAl₂ thus indicating a clear positive correlation between dT_c/dp and the de Gennes factor G. The results are discussed in terms of the RKKY model. However, the phenomenological parameter D/d, where D is the nearest-neighbour R-R distance and d the diameter of the 4f orbital, is used to reflect the non-δ-function character of the sf-coupling parameter Г. The experimental values of Г²D² and T_p/G are found to decrease linearly with increasing D/d. This is in keeping with the RKKY proportionality of $\text{T}{}_{\mathrm{c}}\text{?T}{}_{\mathrm{p}}$ to Γ²E^?1_FG. For GdAl₂, TbAl₂ and DyAl₂ the quantity $\text{?}\text{(}\text{d}\text{T}{}_{\mathrm{c}}\text{d}\text{p}\text{)}\text{k}{}_{\mathrm{l}}\text{(}\text{D}\text{d}\text{)}\text{G}$ coincides within the error limits with the slope of the T_p/G vs D/d plot.     

Crystal field parameters and phase transitions in ErSb

The crystal field levels of the Er ($\text{J =}\text{15}\text{2}$) ion in a single crystal of ErSb have been measured by inelastic neutron scattering. The crystal field parameters obtained by a least squares fit to the spectra at several temperatures are: B₄ = (0·473 ± 0·005) × 10^?2°K and B₆ = (0·59 ± 0·06) × 10^?5°K, which differ considerably from the values o by interpolation from measurements on other compounds. In addition the temperature dependence of the magnetic scattering in the vicinity of the Néel temperature (T_N = 3·55°K) clearly demonstrates that the transition is second order in contrast to the first order behavior suggested by specific heat measurements. Also, any lattice distortion accompanying the magnetic ordering is less than 0.1 per cent, the resolution of the present experiment.     

Heat capacity of a five-coordinated iron(III) complex,chlorobis(N,N-dimethyldithiocarbamato) iron(III), between 0.4 and 300 k: New finding of a magnetic phase transition

The heat capacity of the title complex, Fe[S₂CN(CH₃)₂]₂Cl, has been measured between 0.4 and 300 K. A λ -type phase transition with a small shoulder arising from magnetic ordering was found at (0.609 ± 0.005) K. The character of the ordered phase has been suggested to be ferromagnetic on the basis of comparison between the methyl- and ethyl-homologues. The magnetic hyperfine structure of the Mössbauer spectra and the line broadening due to electronic relaxation effects at 1.2 K hitherto reported are concluded to result from a critical slowing-down when the magnetic transition temperature is approached from the high-temperature side. A Schottky-type anomaly arising from the zero-field splitting of a single ferric ion was observed around 2 K. The excess entropy beyond the lattice contribution at low temperatures amounts to (14.05 ±0.27) J K^?1mol^?1, which cannot be accounted for solely by the magnetic entropy of Rln 4 (= 11.53 JK^?1mol^?1) for the intermediate spin of $\text{S =}\text{3}\text{2}$. Two possibilities concerning additional conntribution have been discussed; one is a mixing of spin species of $\text{S =}\text{5}\text{2}$ and the other is a tunnel-splitting of the rotational levels of four methyl-constituents. The present study cannot give a definite conclusion as to the existence of dimeric units suggested from Mössbauer spectroscopy.     

Specific heat of Ni(ClO4)26H2O between 2 and 17 K

A specific heat investigation of nickel perchlorate hexahydrate was performed between 2 and 17 K. Lattice vibration and magnetic contributions were separated. The lattice term obeys a Debye αT³ law, with $\text{α = 4.04 × 10}{}^{\mathrm{?3}}\text{J}\text{K}{}^4$ mol. The magnetic contribution comes from the splitting of the ground state triplet of the Ni²⁺ ions, by axial and rhombic crystal field distortions, which can be explained by a Schottky specific heat with D = 1.72 KandE = 0.06 K.     

Decoupled magnetic subsystems in the random mixture FepCo1-p(C5H5NO)6(ClO4)2

Specific heat data on the random mixtures Fe_pCo_1-pL₆(ClO₄)₂, where L = C₅H₅NO, are presented. The Fe and Co magnetic atoms have competing anisotropies since the pure Fe and Co compounds are known to be good examples of the simple cubic, $\text{S =}\text{1}\text{2}$, Ising and XY magnet, respectively. The experimental data show the two magnetic subsystems in the mixtures to be almost completely decoupled, which is a consequence of the fact that the crystal field anisotropies of the Fe²⁺ and Co²⁺ ions, yielding g_∥ ? g_⊥ and g_⊥ ? g_∥, respectively, are very strong compared to the magnetic exchange interactions. Consequently the two magnetic subsystems experience one another as nonmagnetic impurities. A model is presented which explains these results, as well as those previously found for related random mixtures, in terms of two interpenetrating percolation clusters.     

Magnetic properties of the rare-earth diborodicarbides (RB2C2)

The magnetic susceptibility of RB₂C₂ has been measured in the temperature range of 3–300 K. Curie-Weiss fits to the susceptibilities led to effective moments in agreement with those expected for R³⁺ ions. The RB₂C₂ (R = Ce, Nd, Sm, Gd, Tb, Er, and Tm) compounds are antiferromagnetic. Metamagnetic transitions at low fields were observed for CeB₂C₂ and TbB₂C₂. The compounds, DyB₂C₂ and HoB₂C₂, are ferromagnets with complex magnetic structures. Praseodymium borocarbide becomes a Van Vleck paramagnet at low temperature. The magnetic ordering temperatures of these compounds are discussed in terms of their crystal structure and the RKKY theory.     

The elastic behaviour of the ternary zincblende structure semiconductor CuGe2P3

A single crystal has been grown of CuGe₂P₃, a ternary semiconductor with a zincblende structure in which the copper and germanium atoms are randomly distributed on the cation sites. The second order elastic constants measured by the ultrasonic pulse echo overlap technique (C₁₁ = 13.66, C₁₂ = 6.17, C₄₄ = 6.66 and bulk modulus B = 8.67 in units of 10¹⁰Nm^?2 at 291 K) are closely similar to those of GaP and conform well to Keyes' correlation for zincblende structure crystals. The hydrostatic pressure derivatives of the second order elastic constants ($\text{?C}{}_{11}\text{?P}\text{= 4.40}$, $\text{?C}{}_{12}\text{?P}\text{= 3.9}$, $\text{?C}{}_{44}\text{?P}\text{= 0.93}$ and $\text{?B}\text{?P}\text{= 4.07}$) and the third order elastic constants (C₁₁₁ = ? 8.45, C₁₁₂ = ? 3.49, C₁₂₃ = ? 1.13, C₁₄₄ = ? 2.82, C₁₅₅ = ? 1.44 and C₄₅₆ = ? 0.69 in units of 10¹¹Nm^?2) also resemble those of GaP: even the anharmonicity of the long wavelength acoustic modes of this ternary semiconductor resembles that of its binary “parent” compound. The positive signs of the hydrostatic pressure derivatives and the negative signs of the third order elastic constants show that the acoustic modes at the long wavelength limit stiffen under pressure, an effect which is quantified here by computation of the mode Grüneisen parameters, which are all positive. The harmonic and anharmonic force constants, obtained in the valence force field model, fit well into the pattern shown by related zincblende structure compounds: the ratio ($\text{β}\text{α}$) for bond bending (β) to stretching (α) force constants is greater than 4:1; the dominating anharmonic force constant is γ: most of the anharmonicity is associated with nearest neighbour atoms. Analysis of the temperature dependence of the elastic constants on the basis of a simple anharmonic model again emphasises the similarity between the elastic behaviour of CuGe₂P₃ and GaP. The thermal expansion of CuGe₂P₃ varies almost linearly with temperature between 291 K and 1000 K, the linear coefficient of thermal expansion α being 8.21 ± 0.02 × 10^?6 °C^?1. The similar lattice parameters and elastic behaviour of CuGe₂P₃ and GaP indicate that semiconducting devices made of epitaxial deposits of CuGe₂P₃ on a GaP substrate should prove to be almost strain-free.     

The crystal structures of the ion conductors (NH+4)Zr2(PO4)3and (H3O+)Zr2(PO4)3

The crystal structures of (NH⁺₄)Zr₂(PO₄)₃ and (H₃O⁺)Zr₂(PO₄)₃ have been determined from neutron time-of-flight powder diffraction data obtained at 15 K. Both compounds are rhombohedral, $\text{R}\text{3}\text{c}$, with cell parameters a=8.7088(1) and c=24.2197(4) Å for the ammonium compound and a=8.7528(2), c=23.6833(11) Å for the hydronium compound. In both cases the ions are completely localized in the type I cavities and hydrogen bonded to lattice oxygens. The measured unit cell parameters are relatively large for this class of compounds but the entrance ways into the cavities are still too small to allow for unrestricted movement of the ions. Thus the low conductivity of the hydronium ion is related to this and other structural features.     

Ferromagnetic ordering in the MMnF6 series (M = Ni,Cu, Zn,Pd)

Neutron diffraction experiments performed on MMnF₆ compounds (M = Ni, Cu, Zn, Pd) have shown that both NiMnF₆ and ZnMnF₆ crystallize in the rhombohedral R$\text{3}$ space group with a cationic ordering, whereas PdMnF₆ shows cationic disordering (R$\text{3}$c, a = 5.46 Å, α = 54.45°). CuMnF₆ has a monoclinic distortion derived from the MnF₃ structural type (a = 8.57 Å, b = 4.85 Å, c = 13.46 Å, β = 92.12°). The magnetic properties can be correlated with the structure: the R$\text{3}$ ordered compounds show a ferromagnetic behavior (T_C(NiMnF₆) = 39 K; T_C(ZnMnF₆) = 9.5 K; T_C(CdMnF₆) = 8 K), while the other two have an antiferromagnetic ordering.     

Single crystal preparation and crystalline electric field parameters of ErAl2

For the first time the preparation of single crystals of ErAl₂ and some isostructural compounds is described. From recently reported susceptibility measurements on ErAl₂ single crystals the parameters of the crystalline electric field are calculated to beB ₄=+15·10^?4°K±30% andB ₆=?2.1·10^?6 °K±30%. These parameters are discussed in terms of the point charge model. This model describesB ₄ andB ₆ and the magnetic properties of ErAl₂ in good approximation.     

Crystal field effects in PrAl2

We re-examine the crystal field interpretation of inelastic neutron scattering results on PrAl₂. With the crystal field parameters x = 0.75 and W = 0.315 meV and the molecular field parameter $\text{λ}\text{=}\text{145 kOe}\text{μ}\text{B}$ we can explain the crystal field effects of susceptibility, spontaneous magnetization, specific heat capacity and electrical sensitivity of PrAl₂ rather well.     

Crystal growth,structure, electron paramagnetic resonance and magnetic properties of (NH4)2V3O8

A method to grow single crystals of ammonium vanadate (IV, V) (NH₄)₂V₃O₈ has been devised. The crystal structure is tetragonal P4bm; residual factor is R = 0.030. Cell parameters are $\text{a = 8.891 ± 0.004}\text{A}\text{?}$ and $\text{c = 5.582 + 0.002}\text{A}\text{?}$. The V⁵⁺ atom lies at the center of a triangular pyramide (VO₄ tetrahedron) while the V⁴⁺ atom is on A 4-fold rotation axis at the center of a square-based pyramide VO₅ whose symmetry point group is almost C_4v with the short V = O bond lying along the 4-fold axis parallel to the c edge of the tetragonal cell. Crystals are thin platlets with (001) cleavage planes. The platlets have very often a square or rectangular shape limited by {100} or {110} planes. Each single crystal was not large enough to record a good e.p.r. spectrum, but by sticking on the same quartz plate a score of them it was possible to gather enough crystals so to record correct spectra and by orienting the plate to obtain resonance lines separately for g_∥ = 1.9263 et g_τ = 1.9755. Measurements at 283 K on powder samples gave times for spin-spin relaxation T₂ = 0.4 × 10^?7s and for spin-lattice relaxation T₁ = 1.6 × 10^?7s. The magnetic structure is characterized by an exchange narrowing ω_e = 3 × 10¹⁰rad/s which corresponds to a transition temperature of about 0.5 K. Static susceptibility measurements at high magnetic field show a paramagnetic behaviour with an antiferromagnetic interaction which is interpreted in the magnetic space group P_2c4bm as the interaction between V⁴⁺ ions from consecutive planes parallel to (001).     

Heat capacity and thermodynamic properties of α-Fe2O3 in the region 300–1050 K. antiferromagnetic transition

The heat capacity of synthetic α-Fe₂O₃ has been measured in the range 300–1050K by adiabatic shield calorimetry with intermittent energy inputs and temperature equilibration in between. A λ-type transition, related to the change from antiferro- to paramagnetism in the compound, is delineated and a maximum heat capacity of about 195 JK^?1 mole^?1 is observed over a 3 K interval around 955 K. Values of thermodynamic functions have been derived and C_P (1000K), [H⁰(1000K)-H⁰(0)], and [S⁰(1000K)-S⁰(0)] are 149.0JK^?1 mole^?1, 115.72 kJ mole^?1, and 252.27 JK^?1 mole^?1, respectively, after inclusion of earlier low-temperature results [X⁰ (298.15K)-X⁰(0)]. The non-magnetic heat capacity is estimated and the thermodynamic properties of the magnetic transition evaluated. The results are compared with spin-wave calculations in the random phase approximation below the Néel temperature and the Oguchi pair model above. An upper estimate of the total magnetic entropy gives 32.4JK^?1 mole^?1, which compares favorably with that calculated for randomization of five unpaired electron spins on each iron, ΔS = 2R ln 6 = 29.79 JK^?1 mole^?1 for α-Fe₂O₃. The critical exponent α in the equation $\text{C}{}_{\mathrm{m}}\text{= (}\text{A}\text{α}\text{) [(|T}{}_{\mathrm{<mtext>n</mtext>}}\text{?T|/T}{}_{\mathrm{<mtext>n</mtext>}}\text{)?1]}{}^{\mathrm{?\alpha }}\text{+ B}$ is ?(0.50±0.10) below the maximum and 0.15±0.10 above, for T_n = 955.0K. The high temperature tail is discussed in terms of short range order.     

Electronic transition moments between excited singlet states of the H2 molecule

The twelve transition moments which connect each of the three ¹Σ_g⁺ states EF, GK, and $\text{H}\text{H}$ with the three ¹Σ_u⁺ states B,B′, $\text{B″}\text{B}$ and with the state C¹Π_u were computed in the range of internuclear distances 1.25 ≤ R ≤ 15 a.u. using accurate electronic wavefunctions. The relative phases of the wavefunctions, which determine the signs of the transition moments, were consistently defined at all R values. The strong R dependences of the transition moments reflect the R-dependent changes in electronic character of the states involved in these transitions. At large R values the ¹Σ_g⁺-¹Σ_u⁺ transition moments are dominated by the two-electron charge resonance in the ionic configuration H⁺ + H^? whose transition moment is $\text{M(R) ? R}$.     

Two-dimensional spin ordering in YFe2O4

A neutron diffraction study was performed on a single crystal of a new compound YFe₂O₄ below its Néel point. In a slightly oxygen deficient crystal, the elastic magnetic scattering takes the form of Bragg line along the c axis at $\text{(}\text{n}\text{3}\text{,}\text{n}\text{3}\text{, l) (n ≠ 3m)}$ in the hexagonal lattice. This fact indicates the two-dimensional long range order of a commensurate sinusoidal spin structure.     

Thermal and magnetic studies of the nearly one-dimensional antiferromagnetic system CsNiBr3

Magnetic susceptibility, specific heat and ¹³³Cs magnetic resonance measurements in a single crystal of CsNiBr₃ are reported. The data reveal two magnetic transitions separating the paramagnetic phase from the antiferromagnetic ground state. At the higher transition temperature T_N2 = (14.25 ± 0.05)K a net magnetic moment is observed only along the hexagonal c-axis, while only below the lower transition temperature T_N1 = (11.75 ± 0.05)K a perpendicular component of the magnetic moment appears also. Above T_N2 CsNiBr₃ can be described as a one-dimensional antiferromagnet with intrachain exchange interaction $\text{J}\text{k}{}_{\mathrm{B}}\text{= ?(17.0 ± 0.2)}\text{K}$ and single-ion anisotropy constant $\text{D}\text{k}{}_{\mathrm{B}}\text{? ?1.5}\text{K}$. Below T_N1, the data are consistent with the non-colinear triangular structure of the Ni²⁺ moments proposed previously for the isomorphic crystal CsNiCl₃. A reduced value of the zero-temperature susceptibility over the classical value is found and atrributed to the zero point deviations.     

Heat capacity of a cubane-tetramer, [Ni(OCH3) (SAL) (CH3OH)]4, between 0.4 AND 288 K: spin-spin interactions and tunnel-splitting of the internal rotation of methyl-groups2

The heat capacity of a cubane-tetramer, tetra-μ₃-methoxy-tetrakis [salicylaldehydato (methanol) nickel (II)] (abbreviated as [Ni(OCH₃) (SAL) (CH₃OH)]₄), has been measured from 0.4 to 288 K. A broad peak centered at 0.85 K was observed. Subtraction of the lattice heat capacity from the observed one brought about another broad peak centered around 13.5 K. The magnetic anomaly is accounted for by a nearest-neighbor intracluster ferromagnetic exchange interaction characterized by $\text{J}\text{k}\text{= 3.8 K}$ and a single-ion zero-field splitting due to biaxial crystalline anisotropy$\text{(}\text{D}\text{K}\text{= 3.8 K}$ and$\text{E}\text{k}\text{= 1.9 K).}$ The tunnel-splitting of the ground vibrational-rotational state is δ = 2.4 J mol^?1, which corresponds to a potential barrier of V₀ = 2.3 kJ mol^?1 when a three-fold symmetry of a methyl-rotator is assumed. Comparison of the heat capacities between the present compound and a similar cubane-tetramer, [Ni(OCH₃) (acac) (CH₃OH)]₄, indicates that among eight methyl-groups the four belonging to methoxy-ligands are concerned with the tunnel-splitting at low temperatures.