On the behavior of Ho3+ in LaCl3 and the correlation with its absorption spectra

The crystal field (CF) energies of the electronic ground state of Ho³⁺ ions in a LaCl₃ host have been calculated with the set of CF parameters of Crosswhite et al. The magnetic anisotropy and the average susceptibility have been studied from room temperature down to liquid helium temperature. The g-values and the hyperfine structure parameters have been computed and compared with the experimental values. The Schottky and hyperfine heat capacities have also been determined and some interesting anomalies are predicted. All available observed properties are explained fairly well on the basis of the interaction of the ion with the CF proposed by Crosswhite et al.     

Crystal field investigations of Yb(C2H5SO4)3. 9H2O and Er: YA1G

Using the spectroscopically derived crystal field parameters for Yb(C₂H₅SO₄)₃. 9H₂O and Er³⁺: YA1G, the temperature dependence of Schottky specific heat, paramagnetic susceptibility, magnetic anisotropy and μ_eff has been calculated over a temperature range 5–400°K. The hyperfine interaction parameters for ¹⁷¹Yb³⁺, ¹⁷³Yb³⁺ and ¹⁶⁷Er³⁺ systems are also obtained and in turn used to estimate the nuclear specific heat. The nice agreement obtained for susceptibility and specific heat of Yb(C₂H₅SO₄)₃. 9H₂O at very low temperatures confirms the accuracy of CEF parameters employed and the neglect of exchange interaction. However, for Er³⁺: YA1G, the CEF parameters are adequate to explain the bulk thermal and magnetic properties but not the g-values.     

Magnetic measurements on single crystals of Ho(CF3SO3)3.9H2O and crystal field investigation

Magnetic measurements on single crystals of holmium trifluoromethanesulfonate (HoTFMS) have been carried out from 300 to 12.5 K. The hexagonal crystal structure of HoTFMS is very similar to that of the hydrated rare earth ethylsulfates with the non-Kramers Ho³⁺ ion occupying a site of C_3h symmetry. A very good theoretical simulation of the principal magnetic susceptibilities, observed by us and the Friedberg group, over the wide range 300 to ∼1.0 K was obtained with the crystal field J-mixed eigenvectors taking into consideration intermediate coupling effects. No ordering effects were noticed by us down to ∼12.5 K indicating the interionic interaction to be of predominantly dipolar type consistent with the discovery of a ferromagnetic transition at T∼0.23 K by the Friedberg group. The g-values are found to be in reasonable agreement with those derived from other sources. The Schottky anomaly in the electronic heat capacity observed at ∼6 K by the Friedberg group is borne out excellently by our theoretical values computed from the crystalline Stark pattern. The thermal behavior of quadrupole splitting and hyperfine heat capacity is calculated and our computed values explain very well the principal anomaly in C_N observed experimentally.     

Crystal field investigation on the magnetic properties of Yb in Yb(CF3SO3)3·9H2O

Ytterbium tri-fluoromethanesulfonate (YbTFMS) single crystals are prepared from the slow evaporation of the aqueous solution of YbTFMS and the principal magnetic susceptibility perpendicular to the c-axis of the hexagonal crystal (χ_⊥) is measured from 300 K down to 13 K. Principal magnetic anisotropy Δχ(=χ_∥−χ_⊥) is measured from 300 K down to 80 K which provides principal magnetic susceptibility parallel to the c-axis (χ_∥) down to 80 K. Very good theoretical simulation of the observed magnetic properties of YbTFMS has been obtained using one electron crystal field (CF) analysis having C_3h site symmetry. No signature of ordering effect in the observed magnetic data is noticed down to the lowest temperature (13 K) attained, indicating the inter-ionic interaction to be of predominantly dipolar type. The calculated g-values are found to be g_∥=2.67 and g_⊥=2.51, respectively. CF analysis provides the electronic specific heat which gives two Schottky anomalies in its thermal variation down to ∼13 K. The temperature dependences of quadrupole splitting and hyperfine heat capacity are studied from the necessary information obtained from the CF analysis.     

Magnetic behavior of Dy3+ Ion in Dy2(SeO4)3 · 8H2O. Experimental and theoretical study including the effects of J-J mixing

Single crystals of dysprosium selenate octahydrate were grown and magnetic measurements carried out on the principal anisotropies and the principal susceptibility χ₁ at room temperature and their thermal variation down to 90 K. The magnetic moment is found to be slightly lower than the free-ion value, although the anisotropy is quite high. The variation of the average moment with temperature is very small and a least squares fit to a Curie-Weiss law yielded ?0.97 K as the paramagnetic Curie temperature. An analysis of the data was undertaken on the basis of interaction of the rare earth ion with its immediate neighbors. A crystal field (CF) of tetragonal symmetry which is the approximate site symmetry of the RE³⁺ ion, gave an excellent simulation of the observed behavior. Considerable effects of J-J mixing of the first three J-multiplets with the ground one were noticed. g-factors and the Schottky anomalies in the heat capacity were determined theoretically. Various hyperfine properties, including the thermal variation of the Mössbauer spectra, were computed for both isotopes of dysprosium in the light of the proposed CF.     

Low temperature studies on magnetic properties of Tm2O3

Magnetic properties of Tm₂O₃ were studied by means of magnetometry as well as by heat capacity measurements. The specific heat data were collected down to 0.35 K, and yielded some new information about crystal field splitting of the ³H₆ thulium multiplet. Some anomalous behaviour of the specific heat below 5 K was observed. It turned out, that this anomaly can be nicely described by Schottky contribution originating from crystal field levels distribution of the Tm³⁺ multiplet. No magnetic ordering was evidenced down to the lowest temperatures studied.     

Crystal-field effect on the hyperfine splittings,Mössbauer spectra and specific heat of Er3+ in pyrogermanate and diglycollate hosts

Hyperfine splittings and the Mössbauer spectra (MS) of the two isomers ¹⁶⁶Er and ¹⁶⁷Er in the pyrogermanate (or ErPG) and diglycollate (or ErDG) hosts were calculated using the previously determined values of the crystal field (CF) parameters and the CF levels. MS for the 166 isomer in both the hosts show only 5 lines, whereas 27 lines are expected for the 167 isomer. In case of ErDG, the quadrupole interaction P increased considerably between 300 and 4 K, i.e., from 1.5 to 21.3 MHz in case of ¹⁶⁶Er and from −1.0 to −14.0 MHz in ¹⁶⁷Er. However for ErPG, the corresponding changes in P for both the isomers are insignificant ∼1 MHz. The hyperfine magnetic fields H_hf in ErDG and ErPG were found to be nearly the same being equal to 4.4±0.01 MG because the g_∥-values are close, i.e., 10.31 and 10.58, respectively. Specific heat C_p of ErPG was measured between 30 and 0.65 K and a sharp λ peak was detected with a transition temperature T_N=0.95±0.01 K. The calculated hyperfine and Schottky specific heat components, C_hf, and C_sch, respectively showed peaks at 32 mK and 110 K. From the experimental results of C_p, the lattice specific heat C_L/R in ErPG was found to be 3.34×10⁻⁵ T³ and the thermal characteristics of the magnetic specific heat C_M was determined. The internal energy U_M(T) was obtained from C_M by numerical integration and its change ΔE/R=[U_M(∞)/R–U_M(0)/R] was found to be 1.02 K and the corresponding value of the Weiss constant θ in the ordered state was 2.01 K. The value of the exchange interaction constant |J_ex/k| and the dipole–dipole interaction constant for nearest neighbours were found to be ∼0.5 and ∼1.03 K, respectively. The molecular field (H_mol) for ErPG was equal to 4.1 kG. From future epr and MS measurements, interesting results are expected regarding the magnetic ordering in ErPG and the phase change in ErDG.     

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.     

Specific heat of dysprosium gallium garnet between 37 mK and 2 K

The specific heat of a single crystal of dysprosium gallium garnet (Dy GaG) has been measured between 37 mK and 2 K using a double-stage demagnetization cryostat. An antiferromagnetic ordering occurs at T_N = 0.373 K. The value of the entropy at 2 K indicates that the ground state is a Kramers doublet. At lower temperatures, a hyperfine contribution is seen. The anomalously large specific heat observed above 0.4 K is interpreted in terms of the lambda-anomaly tail and a short range contribution with a rounded maximum at about 0.7 K.     

The Nd–Mn exchange interaction,low temperature specific heat and magnetism of Nd2/3Ca1/3MnO3

The low temperature specific heat and magnetic characteristics of Nd_2/3Ca_1/3MnO₃ perovskite are studied in a wide range of magnetic fields (up to 9 T). Temperature dependent specific heat data show a broadened Schottky-like anomaly below 20 K caused by splitting of the Nd³⁺ ions ground-state doublet in the effective molecular field H_ex, determined by exchange interaction between Nd and Mn spin systems supplemented by an applied external magnetic field. Existence of the splitting at zero magnetic field and expressed field dependence is the evidence of a strong exchange coupling between Nd and Mn magnetic subsystems. The Nd-ions magnetic ordering leads to an additional contribution to the magnetic moment of the system below 30 K, producing anomalies of the magnetic loss and field-cooled and zero-field-cooled magnetizations. The observed broadened Schottky-like anomalies are fitted for each applied magnetic field by the sum of three Schottky functions. Applied magnetic field extends the anomaly region and shifts it to higher temperatures. Splitting of the higher crystal field Kramers doublets gives an additional contribution to the heat capacity in magnetic fields. The ground state doublet g-factors g_|| and g_⊥ were estimated to be 3.4 and 2.2, respectively, and H_ex was estimated to be 9 T. The Nd³⁺ ions magnetic moment estimated from the magnetization data agrees with the value obtained from the specific heat data.     

Relaxation effects in Mössbauer spectra of bridged seven-coordinate Fe3+ pairs

The compound [Fe₂L(H₂O)₄] (ClO₄)₄.H₂O which contains pairs of Fe³⁺ ions within a binucleating macrocycle derived from Schiff base condensation of 2,6-diacetylpyridine and 1,3-diamino-2-hydroxy-propane has been studied by magnetic susceptibility measurements and⁵⁷Fe Mössbauer spectroscopy between 4.2 K and 300 K, and its crystal structure determined. The spectra show relaxation effects at all temperatures. Spectra taken at 4.2 K in applied fields of about 3 T showed thatV _zz is positive and η～0. The spectra were fitted using a stochastic model of a magnetic hyperfine field relaxing parallel to thez axis, giving relaxation times of 10^?9?10^?10 s.     

NDMAP: the best material to study the Haldane's prediction

As predicted by Haldane, spin, S=1 one-dimensional (1D) Heisenberg antiferromagnet (HAF) has an energy gap between the singlet ground state and first excited triplet. On application of magnetic field, the triplet state Zeeman splits and the energy of one of the triplet state becomes zero at a critical field, H_c. Above H_c the system recovers magnetism. Then, we expect that a quasi-1D HAF will show a magnetic long-range ordering (LRO) at low temperatures due to the inter-chain coupling. This field-induced LRO has not been observed before due to complication of the crystal structure in the materials studied so far and/or technical difficulty.From a heat capacity measurement on a single crystal of an S=1 quasi-Q1D HAF, Ni(C₅H₁₄N₂)₂N₃(PF₆), we found an anomaly at a temperature in finite fields indicating a field-induced phase transition. A magnetic LRO is confirmed by a neutron diffraction measurement on the same sample. The temperature versus magnetic field phase diagram of this compound is constructed and discussed.     

Calorimetric study of N-isopropyl carbazole single crystals in the range 125–240 K

The specific heat (C_p) of N-isopropylcarbazole crystal has been measured in the temperature range 125–240 K by differential scanning calorimetry. A sharp endotherm was found at 137 K (ΔH = 123 cal·mol⁻¹), confirming the occurrence of a first order phase transition, recently reported in literature. Another interesting finding is a ∼ 10% rise of C_p between 170 and 200 K which might be associated with another (non-first order) phase transition.     

161Dy Mössbauer study on magnetic properties in DyZn2 intermetallics

The magnetic properties of the DyZn₂ have been studied by¹⁶¹Dy Mössbauer effect measurements at temperatures from 5.0 to 77.4 K. The spectra are interpreted with a single set of hyperfine parameters. The magnetic hyperfine field is 837 MHz at 5 K, which is very close to the value of Dy³⁺ free ion. Since the relaxation rate increases rapidly as the temperature increases, no accurate hyperfine parameters are obtained analytically nearT _N. The width of the Lorentizian absorption lines increases at the temperatures at which the magnetic structure is an incommensurable moment-modulated one. Anomalies in the -ray transmission rate at zero velocity are observed at 29 and38 K which are the commensurate-incommensurate transition andthe Néel temperatures, respectively. Another anomaly observed around 60 K may originate in a short-range order of Dy moments.     

Gamma-radiolysis of deaerated cysteine solutions

The electron paramagnetic resonance (EPR) spectra of gamma-irradiated single crystals of phenidone (fenidon C₉H₁₀N₂O) have been studied for different orientations of crystals in a magnetic field. Phenidone single crystals have been irradiated with ⁶⁰Co-γ rays at room temperature. The EPR spectra have been investigated at temperatures between 125 and 450 K. The spectra have been found to be temperature independent. The spin-Hamiltonian parameters have been obtained from the single-crystal EPR analysis. The principal values of the hyperfine coupling tensor of the unpaired electron and the principal values of the g-tensor have been determined.     

Lattice dynamics,phase transitions and spin relaxation in [Fe(C5H5)2] PF6

The organometallic compound ferrocenium hexafluorophosphate, [Fe(C₅H₅)₂] PF₆, has been studied by Mössbauer spectroscopy in the past, mainly to determine the crystal structure at high temperatures. Here we present studies at 95 K to 305 K and analyze the spectra in terms of spin relaxation theory which yields accurately the hyperfine interaction parameters and the spin-spin and spin-lattice relaxation rates in this paramagnetic compound. The spectral area under the resonance curve yields the recoil free fraction and thus the mean square of the vibration amplitude <x²>. One observes a large discontinuity in the slope of <x²> versus T at ?210 K, indicative of a phase transition. The analysis of the spectra proves that the quadrupole interaction is small but certainly negative, ½e²qQ = -0.12(2) mm/s, and causes the asymmetry observed in the spectra. The detailed analysis yields also, for the first time, the fluctuating effective magnetic hyperfine field, H _eff = 180(50) kOe.     

Magnetostriction measurements of CoS2 single crystal

The magnetorestriction constants of CoS₂ single crystal were measured by a capacitance method in a temperature range from liquid N₂ to the Curie temperatures.The constants γ₁₀₀ and γ₁₁₁ are ?1.9 × 10^?6 and 5.7 × 10^?6 at liquid N₂ temperature respectively, and the absolute values of the constants decrease monotonically with the increase of the temperature. The volume magnetorestriction constant δω/δH at 110 K in the ferromagnetic state is 6 × 10^?10 Oe^?1.     

Magnetic order in Y6(57Fe:Mn)23H26

The ferrimagnetic compound Y₆Mn₂₃ and its hydride Y₆Mn₂₃H₂₆, both doped with 0.5%⁵⁷Fe, have been investigated using the ⁵⁷Fe Mössbauer resonance and dc field magnetization measurements. For the hydride a small ⁵⁷Fe magnetic hyperfine field is observed to increase abruptly below 110 K whereas the bulk magnetization results suggest antiferromagnetic ordering at T_N≈ 180 K.     

Crystal field interactions in DyFe2Si2 and DyFe2Ge2

Two sets of crystal field (CF) parameters have been proposed for DyFe₂Si₂, none of which could provide a simultaneous explanation of the available experimental data, particularly at low temperatures (below 100 K). The set derived from magnetic studies could not even explain the thermal variation of the magnetic specific heat reported in the same work. Although the set of CF parameters, obtained from a fit to the Mossbauer spectra, could provide a fairly good explanation of the thermal variation of the magnetic susceptibilities along the c-axis, it could not explain the observed thermal variation of other reported experimental findings. In the present work, an appraisal of the CF parameters proposed earlier has been done and a set of CF parameters has been derived, which provide a simultaneous explanation of all the available experimental data. The effect of substitution of Ge for Si on the magnetic properties and the magnetic specific heat of DyFe₂Si₂ has been studied in the framework of one electron crystal field model. The inelastic neutron scattering studies and EPR measurements are required to check the predicted Stark energies and the paramagnetic resonance g-values.     

Ferrimagnetism and hyperfine interactions in RFe5Al7(R = rare earth)

Magnetization and Mössbauer (⁵⁷Fe, ¹⁵⁵Gd) studies of RFe₅Al₇(R = Y, Sm to Lu, ThMn₁₂ crystal structure) in magnetic fields up to 50 kOe and temperatures 4.1 to 500 K have been performed. The Mössbauer studies yield the distribution of the iron ions among the various inequivalent crystallographic and magnetic sites, the hyperfine fields and their temperature dependence. The magnetization curves display a great variety of unusual magnetic phenomena. Among those; strong anisotropy, magnetic and thermal hysteresis (H_c = 24 kOe for DyFe₅Al₇ at 4.1 K), negative magnetization at low temperatures when the sample is cooled in a magnetic field (even in 1 Oe), compensation points, maxima points and time-dependent magnetization. Most of the phenomena observed can be explained in terms of a spin structure previously suggested for the RFe₆Al₆ compounds, composed of 4 magnetic sublattices. The rare earth moments lie antiparallel to the iron moments in the (j) site and to the ferromagnetic component of a canted antiferromagnetic structure of iron in the (f) site. Iron in the (i) site is nonmagnetic.