The cooperative spin transition in [FexZn1 − x(ptz)6](BF4)2: I. Elastic properties — an oriented sample rotation study by Brillouin spectroscopy

The complete set of seven elastic constants of the Fe(II) spincrossover compound [Fe(ptz)₆] (BF₄)₂ (ptz = 1-propyltetrazole) with crystal symmetry R3i was measured by Brillouin spectroscopy at 300K. The measurement on the plate-like single crystals were performed using an oriented sample rotation technique and the combination of two scattering geometries. For comparison the elastic constants of two isostructural compounds were also measured at 300K: the analogous perchlorate spin-crossover compound [Fe(ptz)₆] (ClO₄)₂ and the zinc complex [Zn(ptz)₆] (BF₄)₂. The knowledge of the elastic constants is neccessary for the calculation of the elastic interaction between the spincrossover molecules, and this is the first time that the complete set of elastic constants of a spincrossover compound has been measured directly.     

Phase transitions and molecular motions in [Zn(NH3)4](BF4)2 studied by nuclear magnetic resonance, infrared and Raman spectroscopy

Middle infrared absorption, Raman scattering and proton magnetic resonance relaxation measurements were performed for [Zn(NH₃)₄](BF₄) in order to establish relationship between the observed phase transitions and reorientational motions of the NH₃ ligands and BF₄⁻ anions. The temperature dependence of spin-lattice relaxation time (T₁(¹H)) and of the full width at half maximum (FWHM) of the bands connected with ρ_r(NH₃), ν₂(BF₄) and ν₄(BF₄) modes in the infrared and in the Raman spectra have shown that in the high temperature phase of [Zn(NH₃)₄](BF₄)₂ all molecular groups perform the following stochastic reorientational motions: fast (τ_R≈10⁻¹² s) 120° flips of NH₃ ligands about three-fold axis, fast isotropic reorientation of BF₄⁻ anions and slow (τ_R≈10⁻⁴ s) isotropic reorientation (“tumbling”) of the whole [Zn(NH₃)₄]²⁺ cation. Mean values of the activation energies for uniaxial reorientation of NH₃ and isotropic reorientation of BF₄⁻ at phases I and II are ca. 3 kJ mol⁻¹ and ca. 5 kJ mol⁻¹, respectively. At phases III and IV the activation energies values for uniaxial reorientation of both NH₃ and of BF₄⁻ equal to ca. 7 kJ mol⁻¹. Nearly the same values of the activation energies, as well as of the reorientational correlation times, at phases III and IV well explain existence of the coupling between reorientational motions of NH₃ and BF₄⁻. Splitting some of the infrared bands at T_C2=117 K suggests reducing of crystal symmetry at this phase transition. Sudden narrowing of the bands connected with ν₂(BF₄), ν₄(BF₄) and ρ_r(NH₃) modes at T_C3=101 K implies slowing down (τ_R?10⁻¹⁰ s) of the fast uniaxial reorientational motions of the BF₄⁻ anions and NH₃ ligands at this phase transition.     

Synthesis and characterization of hexakis(acetonitrile)chromium(III) tetrafluoroborate, [Cr(NCMe)6][BF4]3. A nonaqueous Cr source

Oxidation of [Cr^II(NCMe)₄][BF₄]₂ with thianthrinium tetrafluoroborate forms [Cr^III(NCMe)₆][BF₄]₃ exhibiting two ν_CN absorptions at 2331 and 2301 cm⁻¹, and has been structurally characterized with an average Cr-N distance of 1.999 Å. From the electronic absorption spectra the ligand field splitting, Δ₀, is 20,160 cm⁻¹, which is slightly larger than [Cr^III(OH₂)₆]³⁺ in accord with the divalent chromium analogues. The 298 K ESR has a resonance at g=1.9884, and the magnetic susceptibility has a 300 K moment of 3.85μ_B characteristic of S=3/2 Cr(III). The field dependence of the magnetization can be fit to the Brillouin function also characteristic of S=3/2.     

An investigation of FeCoCrO4 by Mossbauer spectroscopy

The spinel FeCoCrO₄ has been studied between 4.2 and 538°K. Characteristic Mossbauer spectra of paramagnetic, magnetic and electronic relaxation types have been observed. The Mossbauer parameters for Fe³⁺ ions situated at tetrahedral (A) and octahedral (B) sites have been calculated. The cation distribution in magnetic and paramagnetic phases is found to be approximately Fe_0.5³⁺Co_0.5²⁺[Co_0.5²⁺Fe_0.5³⁺Cr³⁺]O₄. The Neel temperature been determined by the temperature scanning method to be 310±5°K.     

Crystal structure and ferromagnetism of (n-C3H7)4N[CoFe(dto)3] (dto=C2O2S2)

Recently, we have discovered a new type of first order phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto=C₂O₂S₂), where the charge transfer transition between Fe^II and Fe^III occurs reversibly. In order to elucidate the origin of this peculiar first order phase transition. Detailed information about the crystal structure is indispensable. We have synthesized the single crystal of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃] whose crystal structure is isomorphous to that of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃], and determined its detailed crystal structure. Crystal data: space group P6₃, a=b=10.044(2) Å, c=15.960(6) Å, α=β=90°, γ=120°, Z=2 (C₁₈H₂₈NS₆O₆FeCo). In this complex, we found a ferromagnetic transition at T_c=3.5 K. Moreover, on the basis of the crystal data of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃], we determined the crystal structure of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] by simulation of powder X-ray diffraction results.     

Ground-state properties of LiV2O4 and Li1-xZnx(V1-yTiy)2O4

We present susceptibility, microwave resistivity, NMR and heat-capacity results for Li_1-xZn_x(V_1-yTi_y)₂O₄ with 0 ? x ? 0.3 and 0 ? y ? 0.3. For all doping levels the susceptibility curves can be fitted with a Curie-Weiss law. The paramagnetic Curie-Weiss temperatures remain negative with an average value close to that of the pure compound Θ≈ - 36 K. Spin-glass anomalies are observed in the susceptibility, heat-capacity and NMR measurements for both type of dopants. From the temperature dependence of the spin-lattice relaxation rate we found critical-dynamic behavior in the Zn doped compounds at the freezing temperatures. For the Ti-doped samples two successive freezing transitions into disordered low-temperature states can be detected. The temperature dependence of the heat capacity for Zn-doped compounds does not resemble that of canonical spin glasses and only a small fraction of the total vanadium entropy is frozen at the spin-glass transitions. For pure LiV₂O₄ the spin-glass transition is completely suppressed. The temperature dependence of the heat capacity for LiV₂O₄ can be described using a nuclear Schottky contribution and the non-Fermi liquid model, appropriate for a system close to a spin-glass quantum critical point. Finally an ( x / y , T )-phase diagram for the low-doping regime is presented. Received 16 March 2001 and Received in final form 30 October 2001     

Ab initio molecular dynamics study on Ag (n = 4, 5, 6)

Ab initio Molecular Dynamics (MD) method, based on density functional theory (DFT) with planewaves and pseudopotentials, was used to study the stability and internal motion in silver cluster Ag_n, with n =4-6. Calculations on the neutral, cationic and anionic silver dimer Ag₂ show that the bond distance and vibrational frequency calculated by DFT are of good quality. Simulations of Ag₄, Ag₅, and Ag₆ in canonical ensemble reveal distinct characteristics and isomerization paths for each cluster. At a temperature of 800 K, an Ag₄ has no definite structure due to internal motion, while for Ag₅ and Ag₆the clusters maintain the planar structure, with atomic rearrangement observed for Ag₅ but not for Ag₆. At a temperature of 200 K, Ag₄ can exist in two planar structures whilst Ag₅ is found to be stable only in the planar form. In contrast Ag₆ is stable in both planar trigonal and 3D pentagonal structures. Micro-canonical MD simulation was performed for all three clusters to obtain the vibrational density of states (DOS). Received 5 May 1999 and Received in final form 20 August 1999     

81Br NQR Study of [NH3(CH2) n NH3]CdBr4 (n = 4 and 5) and [NH3(CH2) n NH3]ZnBr4 (n = 5 and 6)

⁸¹Br NQR frequencies and differential scanning calorimetry (DSC) were measured as a function of temperature. [NH₃(CH₂)₄ NH₃]CdBr₄ (1) and [NH₃(CH₂)₅NH₃]CdBr₄ (2) showed a doublet and quartet ⁸¹Br NQR spectrum, respectively. [NH₃(CH₂)₅NH₃]ZnBr₄ (3) and [NH₃(CH₂)₆NH₃]ZnBr₄ (4) exhibited a four-line ⁸¹Br NQR spectrum. From the NQR results, it is inferred that (1) and (2) consist of infinite two-dimensional sheets of corner-sharing CdBr₆ octahedra, whereas (3) and (4) have isolated [ZnBr₄]²⁻ tetrahedra. All of the crystals except (1) showed at least one structural phase transition above 380 K.     

Electrochemical properties of Li[CnF2n+1BF3] as electrolyte salts for lithium-ion cells

The fundamental electrochemical properties of lithium perfluoroalkyltrifluoroborates Li[C_nF_2n+1BF₃] (n = 1∼4) were evaluated as electrolyte salts for lithium-ion battery in comparison with LiBF₄ and LiPF₆. Li[C_nF_2n+1BF₃] showed higher electrolytic conductivities than LiBF₄ in aprotic solvents. In these series, the conductivities decreased with the perfluoroalkyl group being longer, and Li[C₂F₅BF₃] exhibited a comparable conductivity to LiPF₆. The relationship between the conductivity and the anion size showed that the anion with a moderate size is in favor of obtaining high conductivities. The limiting oxidation potentials determined by linear sweep voltammetry demonstrated that Li[C_nF_2n+1BF₃] were less resistant against oxidation than LiBF₄. The HOMO energies and ionization energies of [C_nF_2n+1BF₃]⁻ calculated by ab initio molecular orbital (MO) theory and density functional theory (DFT) supported this observation, however, there was no accuracy to explain the effect of the chain length of perfluoroalkyl groups on the limiting oxidation potentials. The cell performances of a LiC₆/Li_0.5CoO₂ cell using Li[C₂F₅BF₃] were comparable to those using LiPF₆ at room temperature, however, it deteriorated at elevated temperature due to the reaction on the cathode.     

Effect of frustration on the magnetization in nickel ferrite-chromites

A study is reported on the behavior of the isotherms of the magnetization σ(H) and of the longitudinal λ_‖(H), transverse λ_⊥(H), volume ω(H), and anisotropic λ_t(H) magnetostrictions measured at T=80 K in the Cu_0.4Fe_0.6[Ni_0.6Cr_1.4]O₄ and Zn_0.4Fe_0.6[Ni_0.6Cr_1.4]O₄ ferrite-chromites having a frustrated magnetic structure. It has been established that these ferrite-chromites do not undergo technical magnetization and that the growth of the magnetization with the field is accounted for by two paraprocesses of different natures.     

Magnetism in some layer molecular magnets as revealed by Mössbauer spectroscopy

⁵⁷Fe Mössbauer spectroscopy was used to explore magnetic properties of two 2D molecular ferrimagnets. In NPn₄[Fe^IIFe^III(ox)₃] (Pn = n-C₅H₁₁, (ox) =(C₂O₄)^2?), the previously reported negative magnetization is shown here by external field studies to be due to a cross-over between Fe^III and Fe^II- magnetizations. The form and parameters of the magnetic Hamiltonian describing the temperature dependence of both the Fe^III hf-field and net magnetizations has been determined. In NBu₄[Mn^IIFe^III(ox)₃] (Bu = n-C₄H₉) soft XY-magnet the low temperature relaxation spectra are interpreted in terms of slowly varying classical magnetization-evolution at low temperature.     

Doublet and quartet states of Li 2 −

Electronic states of the molecular lithium anion are investigated by configuration-interaction calculations. Comparison with the analogously computed potential energy curves for the lowest singlet and triplet states of the neutral Li₂ shows that in addition to the well-known stable ground state X there also exist metastable excited states of Li ₂ ^- . Within the quartet sector, two candidates for such long-lived states are identified and their spectroscopic properties studied. Received 23 March 1999     

Light-induced absorption change in Fe-doped GaN

The properties of a light-induced absorption (LIA) change were investigated in a semi-insulating Fe-doped GaN crystal. The temporal profile and a spectrum of the LIA were measured in the temperature range from 15 K to 300 K. The LIA was almost proportional to the light intensity and showed slight saturation behavior. The relaxation time constant, in the range of milliseconds, was equal to the lifetime of infrared photoluminescence related to the Fe³⁺ internal transition Fe³⁺(⁴T₁)→Fe³⁺(⁶A₁). The LIA was attributed to an excited-state absorption from Fe³⁺(⁴T₁). Some of the peak energies observed in the LIA spectrum showed good agreement with transition energies expected from an energy diagram of Fe-doped GaN crystal.     

Anelastic relaxation and around the critical Sr content x = 0.02

Anelastic relaxation and ¹³⁹LaNQR relaxation rates in La_2–xSr_xCuO₄ for Sr content around 2 and 3 percent are discussed in terms of spin and lattice excitations and of the related ordering processes. It is argued how the phase diagram of La_2–xSr_xCuO₄ at the boundary between the antiferromagnetic (AF) and the spin-glass phase (x = 0.02) could be more complicate than previously thought, with a transition to a quasi-long range ordered state at K, as indicated by neutron scattering data. On the other hand, the ¹³⁹LaNQR spectra are compatible with a transition to an AF phase around K, in agreement with the phase diagram commonly accepted in literature. In this case the peaks in NQR and anelastic relaxation rates around 150 K and 80 K respectively in La_1.98Sr_0.02CuO₄, yield the first evidence of freezing process involving simultaneously lattice and spin excitations, possibly corresponding to motion of charged stripes. Received 18 May 2000 and Received in final form 11 July 2000     

Magnetic resonance on LiCuVO 4

EPR and ⁷Li NMR measurements were performed in the distorted inverse spinel V(LiCu)O₄ down to 1.5 K. Anisotropy effects on magnetic resonance spectra due to the Jahn-Teller distortion of the oxygen octahedra surrounding the copper ions are discussed. The estimation of the spin-spin interactions deduced from the EPR-relaxation rate Δ H reveals a situation comparable to the prototypical one-dimensional S = 1/2 Heisenberg antiferromagnet CuGeO₃. Approaching three-dimensional antiferromagnetic order ( T _N ≈ 2 K) from above, both magnetic relaxation rates, Δ H _EPR and ⁷ (1/ T ₁ ), respectively, exhibit nearly the same critical divergence reminding to the onset of three-dimensional order in two-dimensional layered systems. Received 22 January 2001 and Received in final form 6 May 2001     

Structure and electrical conductivity of a novel inorganic solid electrolyte: Na14.5[Al(PO4)2F2]2.5[Ti(PO4)2F2]0.5 (NATP)

A novel inorganic solid electrolyte with a layered framework structure stable up to 1043 K, Na_14.5[Al(PO₄)₂F₂]_2.5[Ti(PO₄)₂F₂]_0.5 (NATP), has been hydrothermally prepared and characterized by single-crystal and powder X-ray diffraction techniques, X-ray fluorescence (XRF) analysis, IR spectroscopic measurement, thermogravimetric and differential thermal analysis (TGA and DTA). NATP crystallizes in the acentric hexagonal space group P3 with a=10.448(2), b=10.448(2), , Z=1, containing a large number of Na⁺ cations in the interlamellar space and the cavities of its framework. There are six different crystallographic Na⁺ cationic sites, in which 8% Na(5) and 12% Na(6) sites are vacant. Electrical conductivity measurements show that Na⁺ cations exhibit a high mobility with two domains for the electrical conductivity versus temperature.     

Charge ordering and elastic constants in Fe3-xZnx xO4

We present the temperature dependence of elastic modes of Fe_3-xZn_xO₄ with x = 0, x = 0.02 and x = 0.032. The c₄₄ shear modes show a pronounced softening which can be normalized to a common behavior for all these substances. We can explain the softening with a bilinear coupling of the elastic strain to an order parameter linked to charge ordering processes. The other elastic modes (c₁₁, c₁₂ and the bulk modulus) do not show any softening. We present a symmetry analysis for the charge ordering model. Received 27 April 1999     

Anomalous magnetic behavior of superconducting thin films in small magnetic fields [4] close to the transition temperature

Using a specially designed SQUID magnetometer we measured the temperature dependence of the critical current density in a ring patterned thin film for magnetic fields parallel to the c-axis. In addition, the temporal relaxation of the remanent state as prepared by field cooling in an external field of 100 Oe at different temperatures is determined. The j c ( T ) data show a field-dependent anomalous kink close to T_c pointing to reduced dissipation with increasing temperature allowing to construct a corresponding H-T borderline. A similar behavior is observed for the normalized relaxation rate S ( T ) as extracted from the temporal behavior of the remanent state, which, at low temperatures, exhibits the expected increase for increasing T-values, while an anomalous decrease of S ( T ) is found for temperatures above 85 K. While the low-T regime is attributed to creep of 2D pinned single vortex lines, the high-T behavior is suggested to be dominated by collective motion with a more sluggish dynamics. This change in dynamics is also reflected by the activation barriers for flux creep U ( j ), which show a corresponding crossover in μ from 0.06 to 0.99. An additional scaling analysis of the E-j characteristics for according to vortex glass theory reveals quasi-2D collective creep behavior with . Received: 8 April 1998 / Revised: 15 July 1998 / Accepted: 2 September 1998     

Type-I non-critically phase-matched second-harmonic generation in Gd1-xYxCa4O(BO3)3

Second-harmonic generation was z-cut observed Gd_1-xY_xCa₄O(BO₃)₃ (Gd_1-xY_xCOB) and the dependence of the phase-matching wavelength on the mixing ratio x has been investigated. The dependence on both temperature and angle tuning was examined as well. We found the suitable composition for noncritical frequency doubling at 930 nm, which is the lasing wavelength of Nd:YAlO₃ on the ⁴F_3/2?⁴I_9/2 transition. Received: 19 April 1999 / Published online: 5 May 1999