The 3ν3 overtone bands of UF6 and UF6

The absorption specta of CO laser radiation by 3ν₃ overtone bands of ²³⁸UF₆ and ²³⁵UF₆ has been measured using photoacoustic spectroscopic techniques. For the two temperatures 250 K and 290 K, measured absorption coefficients and cross-sections of the 3ν₃ band of ²³⁵UF₆ are reported for the first time.     

K5Bi(MoO4)4-Nd3+晶体生长和光学性质

在化学计量的熔料里,用提拉法生长了K₅Bi_0.9Nd_0.1(MoO₄)₄和K₅Bi_0.97Nd_0.03(MoO₄)₄单晶。该晶体属于三方晶系,空间群为R3m,Z=1.5,晶胞常数为a=6.023?,c=20.887?(Nd_0.1)。K₅Bi(Mo 关键词：     

Potassium tetracyanoplatinate (II) trihydrate (K2Pt(CN)4·3H2O) studied by high resolution solid state C MAS NMR

Prudent analysis of the solid state ¹³C MAS NMR spectra of polycrystalline K₂Pt(CN)₄ · 3H₂O (KTCP)⁻ reveals that in crystals of this compound there are two types of carbon nuclei with slightly different ¹³C chemical shift tensors, contrary to what is found for the solution NMR spectrum and previous static powder NMR studies on this compound and the high resolution solid state NMR studies on other similar compounds. The ¹³C MAS spectra measured at different rotor spinning speeds are satisfactorily simulated though the use of a newly developed computer program based on a novel density matrix formulation. The present method is eminently successful even though the spectra are rather complicated because of (1) the relatively large anisotropies of the chemical shift tensors; (2) the high-order dipolar interactions between ¹³C and ¹⁴N nuclei because of the strong quadrupolar coupling constants of ¹⁴N nuclei; and (3) the indirect J-coupling between the ¹³C and ¹⁹⁵Pt. The principal elements as well as their orientations of the two ¹³C chemical shift tensors are evaluated from the spectral simulations.     

EPR evidence of local lattice mode in K3H(SO4)2 and Rb3H(SO4)2 fast-proton conductors

The observation of an anomalous temperature dependence of Mn²⁺ EPR spectra linewidth and nonaxial crystal-field parameter in K₃H(SO₄)₂ and Rb₃H(SO₄)₂ allows one to suggest the presence of “local mode” predicted by Yamada (Ferroelectrics 170 (1995) 23). The activation energy for this kind of excitation was found and equals 11.3 (0.5) and 7.4 (0.3) meV for Mn²⁺ doped K₃H(SO₄)₂ and Rb₃H(SO₄)₂, respectively.     

K5Bi0.9Er0.1(MoO4)4的晶体生长和光学性质

在化学计量的熔料里,用提拉法生长了K₅Bi_0.9Er_0.1(MoO₄)₄单晶。该晶体属于三方晶系,空间群为R3m,z=1.5,晶胞参数为a=6.029?,c=20.823?(六方表示)。晶体具有层状结构,沿着(0001)面容易解理。晶体在室温下的吸收光谱包括有若干条吸收带,它们是稀土离子所特有的。其中三个主要的吸收峰分别相当于从Er³⁺离子的基态 ⁴I_15/2向 ⁴G_11/2, ²H_11/2和 ⁴I_13/2能级的跃迁。本文还给出晶体中相当于 ⁴I_13/2→ ⁴I_15/2跃迁的荧光发射光谱。 关键词：     

NMR study of solid C60(γ-cyclodextrin)2

A solid complex of C₆₀ with γ-cyclodextrin (γ-CyD) was examined with NMR spectroscopic methods in order to understand the dynamics of C₆₀, and the interaction between C₆₀ and γ-CyD. A ¹³C solid-state cross-polarization magic angle spinning (CP/MAS) NMR spectra shows C₆₀ resonance at 142.6 ppm. This provides the evidence of interaction between ¹³C spins in C₆₀ and ¹H spins in the γ-CyD host. Ambient temperature experiments on the ¹³C CP/MAS NMR, with varying contact time, shows that the water associated with γ-CyDs plays an important role in the nuclear relaxation processes. The dynamics of C₆₀ in γ-CyD was investigated using temperature and field-dependent ¹³C spin-lattice relaxation time measurements. The influence of water on the dynamics of C₆₀ was less significant below 250 K.     

用同步辐射研究掺Tb3+氟化物K2GdF5的光谱和Gd3+-Tb3+能量传递

对比了不同激发波长下水热法合成的K2GdF5:Tb3+(摩尔分数0.5％)单晶材料的光致发光谱线;监测了5 D3→7F6和5 D4→7 F5的激发谱,给出了几组窄带吸收和3个宽带吸收;分析表明窄带发射为Gd3+的8 S7/2→6FJ、8S7/2→6GJ、8S7/2→6DJ、8S7/2→6IJ的跃迁,宽带发射为Gd3+的...     

Stimulated desorption from CO chemisorbed on Cr(110)

Electron stimulated desorption (ESD) experiments using a time-of-flight pulse counting method are reported for molecular CO chemisorbed on the Cr(110) surface at 90 K. Consistent with previous qualitative observations, negligible CO⁺ and O⁺ desorption signals were measured from the ₁CO overlayer which saturates at 1/4 monolayer. For θ_CO > 0.25, a terminally-bonded (₂CO) binding mode is populated in addition to the existing ∝₁CO binding mode and the ion yield increases sharply. For ₂CO, both O⁺ and CO⁺ ions are observed; the CO⁺ ions desorb with characteristically lower kinetic energies than O⁺ ions. Near saturation coverages of CO(ads), an observed decrease in the O⁺ yield is attributed to adsorbate-adsorbate interactions which reduce the ion desorption probability, as seen in ESD studies of terminally-bonded CO on other metals. These results are considered in the context of two possible models proposed for the ₁CO binding state and related ESD observations for CO chemisorbed on Fe(001) and potassium-promoted Ru(001).     

Study of the ferroelectric–paraelectric phase transition of NaH3(SeO3)2 single crystals by H and Na NMR

The ¹H and ²³Na spin–lattice and spin–spin relaxation times of NaH₃(SeO₃)₂ single crystals grown using the slow-evaporation method were measured as functions of temperature and frequency in the ferroelectric and paraelectric phases. The changes in the symmetry of the (SeO₃)²⁻ dimers as a result of the ferroelectric–paraelectric phase transition are associated with large changes in the spin–lattice and spin–spin relaxation times, and in the number of resonance lines. The large changes in the relaxation times at 195 K indicate that the H and Na ions are significantly affected by this transition. The change in the number of resonance lines for the ¹H and ²³Na nuclei means that the orientations of the (SeO₃)²⁻ dimers and the environments of the Na ions change at T_C. Therefore, the orientations of the (SeO₃)²⁻ dimers and the environments of the Na ions play important roles in the phase transitions. In conclusion, the ferroelectric–paraelectric phase transition of NaH₃(SeO₃)₂ is accompanied by changes in hydrogen-bond structure and distortions of the (SeO₃)²⁻ and Na⁺ ion lattices, which form a slightly distorted octahedron.     

Structure determination, magnetic and optical properties of a new chromium(II) thioantimonate, [Cr((NH2CH2CH2)3N)]Sb4S7

The chromium(II) antimony(III) sulphide, [Cr((NH₂CH₂CH₂)₃N)]Sb₄S₇, was synthesised under solvothermal conditions from the reaction of Sb₂S₃, Cr and S dissolved in tris(2-aminoethyl)amine (tren) at 438 K. The products were characterised by single-crystal X-ray diffraction, elemental analysis, SQUID magnetometry and diffuse reflectance spectroscopy. The compound crystallises in the monoclinic space group P2₁/n with a=7.9756(7), b=10.5191(9), c=25.880(2) Å and β=90.864(5)°. Alternating SbS₃³⁻ trigonal pyramids and Sb₃S₆³⁻ semi-cubes generate Sb₄S₇²⁻ chains which are directly bonded to Cr(tren)²⁺ pendant units. The effective magnetic moment of 4.94(6)μ_B shows a negligible orbital contribution, in agreement with expectations for Cr(II):d⁴ in a ⁵A ground state. The measured band gap of 2.14(3) eV is consistent with a correlation between optical band gap and framework density that is established from analysis of a wide range of antimony sulphides.     

Mössbauer investigations on Np3S5

The 59.5 keV Mössbauer resonance of ²³⁷Np has been measured in Np₃S₅ at 77 and 4.2 K. At 77 K, two different quadrupolar splittings are observed. The first one (δ₁ = −5(1) mm sec⁻¹/NpAl₂) is assigned to the Np⁴⁺ ions and the second one (δ₂ = 28(1) mm sec⁻¹/NpAl₂) is assigned to the Np³⁺ ions. At 4.2 K the spectrum gives a ratio of areas S(Np³⁺)/S(Np⁴⁺) of 2.0. These results clearly confirm the crystallographic data of this mixed-valence material.     

Formation of Mo and MoSx nanoparticles on Au(1 1 1) from Mo(CO)6 and S2 precursors: electronic and chemical properties

Mo(CO)₆ can be useful as a precursor for the preparation of Mo and MoS_x nanoparticles on a Au(1 1 1) substrate. On this surface the carbonyl adsorbs intact at 100 K and desorbs at temperatures lower than 300 K. Under these conditions, the dissociation of the Mo(CO)₆ molecule is negligible and a desorption channel clearly dominates. An efficient dissociation channel was found after dosing Mo(CO)₆ at high temperatures (>400 K). The decomposition of Mo(CO)₆ yields the small coverages of pure Mo that are necessary for the formation of Mo nanoclusters on the Au(1 1 1) substrate. At large coverages of Mo (>0.15 ML), the dissociation of Mo(CO)₆ produces also C and O adatoms. Mo nanoclusters bonded to Au(1 1 1) exhibit a surprising low reactivity towards CO. Mo/Au(1 1 1) surfaces with Mo coverages below 0.1 ML adsorb the CO molecule weakly (desorption temperature<400 K) and do not induce C–O bond cleavage. These systems, however, are able to induce the dissociation of thiophene at temperatures below 300 K and react with sulfur probably to form MoS_x nanoparticles. The formed MoS_x species are more reactive towards thiophene than extended MoS₂(0 0 0 2) surfaces, MoS_x films or MoS_x/Al₂O₃ catalysts. This could be a consequence of special adsorption sites and/or distinctive electronic properties that favor bonding interactions with sulfur-containing molecules.     

Magnetic moments and Fe hyperfine field interactions in Y(Fe1−xRux)2 ternaries

Measurements of magnetization and ⁵⁷Fe Mössbauer spectra have been made for Y(Fe_1−xRu_x)₂. The C15 type cubic structure is stabilized for xx 0.7. The C15 compounds is ferromagnetic with T_c200 K and its saturation moment decreases monotonically with increasing x, while the ⁵⁷Fe hyperfine field decreases only slightly with x. From these results, it is deduced that the Ru atoms have an induced moment of ≈1μ_B in the range x 0.2. In the C14 type phase, no magnetic ordering develops even at 4.2 K.     

A 62 K superconductor with an original structure: Sr4−xBaxTlCu2CO3O7

A new superconductor with an original structure, Sr_4−xBa_xTlCu₂CO₃O₇ has been isolated for 1≤x≤2. It crystallizes in a A-type space group with a=3.84 Å≈a_p, b≈8 × a_p, c≈17.0 Å. The HREM study of this new curprate shows that it derives from the Tl_0.5Pb_0.5Sr₄Cu₂CO₃O₇ structure by a shearing mechanism. Indeed, it can be described as ribbons of the latter structure, four octahedra thick, shifted c/2 with respect to each other. It results in infinite single perovskite layers waving along the (001) plane and connected through flat mixed layers [(TIO)₄(CO)₄]∞. This oxycarbonate can also be described as a 1201-type structure in which the [TIO]∞ layers are replaced by mixed [(TIO)₄(CO)₄]∞ layers. The susceptibility measurements show that this cuprate exhibits a significantly higher critical temperature than the 1201-cuprates. The T_{c onset} of the synthesized phase is 56 K and it can be increased up to 62 K by hydrogen annealing; in the same way, one observes a large Meissner volume fraction of 35% at 4.2 K.     

Inhomogeneous Tl NMR line broadening in Tl2Ba2CuOx single crystals

Temperature and angular dependences of ²⁰⁵Tl line width, Δ , and transverse relaxation time, τ, have been measured in two crystals of Tl₂Ba₂CuO_x with T_c = 32 and 115 K, respectively. In the normal state both Δ and τ have been found to be temperature-independent and not to vary with varying T_c, implying that the size of inhomogeneous broadening is also invariable. Analysis of the line width angular dependence shows that the inhomogeneous broadening originates, most probably, from local distortions associated with Cu substitution for Tl. A conclusion is that variations in T_c are not related to this substitution.     

Analysis of the scattering of 46 MeV protons from Be and C

An analysis is made of the measurements of the elastic and inelastic scattering of 46 MeV protons by ³Be and ¹²C. The optical and collective models are used. There is considerable ambiguity in the optical parameters, and it was not found possible to obtain good fits to cross sections and polarizations simultaneously. Large quadrupole deformations were found for both ¹²C (β₂ ≈ 0.6) and ⁹Be(β₂ ≈ 1). The inelastic scattering from ¹²C agrees best with deformation of both real and imaginary parts of the optical potential, while ⁹Be shows a preference for real coupling. The 14.1 MeV level in ¹²C is interpreted as the 4⁺ rotational state, while the angular distribution for the 7.6 MeV 0⁺ level is well described by double quadrupole excitation via the lowest 2⁺. Interpretations are suggested for other inelastic transitions, including the excitation of spin and isospin oscillations.     

Cl nuclear quadrupole resonance studies of molecular motions of ClO3 and water diffusion in Ca(ClO3)2·2H2O

A ³⁵Cl nuclear quadrupole resonance (³⁵Cl-NQR) investigation of polycrystalline Ca(ClO₃)₂·2H₂O is described. The ³⁵Cl-NQR frequencies (ν_Q) for two resonance lines (ν_Q1 and ν_Q2), the spin lattice relaxation time (T_1Q) for ν_Q2 only and the line width δν_Q2 were measured in the temperature range 292–345 K, except for the frequency measured up to 455 K. The observed decrease in the resonance frequencies with increasing temperature permitted the determination of the frequencies of librations of the ClO₃⁻ ion about two axes perpendicular to the three-fold axis of the ion mainly responsible for this effect. The temperature dependence of the relaxation time T_1Q proved the occurrence of water diffusion and hindered rotation of ClO₃⁻ ions. The activation energies of these two molecular motions were determined, and their effect on the electric field gradient at the site of a chlorine nucleus was discussed. Temperature measurements of the line width δν_Q2 confirmed the conclusions drawn from the analysis of T_1Q(T).     

Magnetic phase transition between ferromagnetic and antiferromagnetic states in Ce(Fe1−xAlx)2

The cubic Laves phase compound Ce(Fe_0.95Al_0.05)₂ exhibits a first order magnetic phase transition from antiferromagnetic to ferromagnetic state at ≈ 100 K with increasing temperature. This note gives the results of the Mössbauer effect of ⁵⁷Fe and the magnetic phase diagram in the external field vs. temperature plane.     

Spectral intensities in the ν1 band of NH3

Intensities have been measured for individual transitions in the Q and R branches of the ν₁ band of NH₃ using a difference-frequency laser spectrometer. The data yield an integrated band strength of S⁰_v=219.36±1.03 cm^-2/MPa at 297 K, corresponding to a transition moment of μ_v = 8.535(20) × 10^-32 C·m, and a Herman-Wallis correction factor, (1 + _jm)², where _j = 0.0209(20). The intensities of a few lines for K 7 were noticeably perturbed by a perpendicular Coriolis interaction with 2ν₄ (E, L = 2), so were excluded from the fit. A small sample of ν₃ band lines occurring in the ν₁ band scans also yields a rough estimate of the ν₃ band intensity with evident irregular perturbations.     

High field Mössbauer investigations of paramagnetic Y(Fe, Al)2

⁵⁷Fe Mössbauer measurements in external fields up to 13.5 T in the temperature range 4–300 K are reported for Y(Fe_xAl_1−x)₂. A negative sign was found for the quadrupole splitting. In the paramagnetic state different induced hyperfine fields for different Fe environments were observed.