87Rb NMR investigations on binary and ternary fullerene compounds: Rb3C60, K2RbC60 and Rb2CsC60

Results of¹³C MAS NMR and⁸⁷Rb NMR measurements on Rb₃C₆₀, K₂RbC₆₀ and Rb₂CsC₆₀ are presented. The⁸⁷Rb NMR spectra show generally the same characteristics as already reported by other authors. For the ternary compound the degree of site preferential order of the alkali metal ions agrees with the analysis of X-ray absorption data. Furthermore, in the room temperature⁸⁷Rb NMR spectra of all samples an additional broadened line is detected indicating that at least for the samples prepared from sublimed C₆₀ a considerable amount of the Rb ions is located on sites with symmetry lower than cubic.     

Energetics and structural stability of Cs3C60

Using the ab initio pseudopotential total-energy method and the density-functional theory, we study the energetics of face-centered-cubic Cs₃C₆₀ which is a material of great interest as a possible high transition-temperature superconductor. At the optimized lattice constant the volume per C₆₀ is found to be smaller than the the most-stable hexagon-coordination A15 phase, while the total energy of the fcc phase is about 0.9 eV higher than the A15 phase. These results indicate that a low-temperature and high-pressure synthesis method might be a possible way to produce the fcc Cs₃C₆₀ phase. In addition, it is also found that the A15 Cs₃C₆₀ should show a phase transformation from a hexagon-coordination phase to a pentagon-coordination phase under hydrostatic pressure.     

The interaction of Cs and O2 on the basal plane of MoS2

The interaction of Cs and O₂ on MoS₂(0001) has been studied both in the alternate adsorption and the codeposition mode by LEED, AES, TDS and WF measurements at 170 and 300 K. Oxygen does not interact with Cs when θ_Cs?0.04 at 300 K or θ_Cs?0.08 at 170 K, where Cs is known to adsorb as strongly ionized, individual adatoms. The interaction at higher θ_Cs, where Cs is known to form clusters on MoS₂(0001), leads to clusters of a Cs/O complex characterized by a Cs(563 eV)/O(512 eV) Auger peak ratio of 1.1–1.3. The minimum WF is 2.1 eV at 300 and 170 K upon alternate adsorption, and 1.7 eV at both T upon codeposition. Upon heating, oxygen and Cs desorb independently, as no oxide desorption is observed. The Cs TDS spectrum is shifted to lower T in the presence of oxygen and a new desorption peak appears at ～ 880 K. The differences in the Cs/O interaction between MoS₂(0001) and other semiconductors and metals are attributed to the Cs clustering and the inertness of MoS₂(0001) to O₂ adsorption.     

Polymeric sheets in Mg4C60

We present preliminary results on the preparation and structure of Mg₄C₆₀, a new fulleride polymer. A series of Mg_xC₆₀ compositions (0<x<6) were prepared by solid state reaction. While most samples were multiphase, a single phase material was obtained at the nominal composition Mg₄C₆₀. The X-ray diffraction pattern of Mg₄C₆₀ was successfully indexed and fitted to a rhombohedral structure based on two-dimensional polymeric sheets of C₆₀ ions. This result extends the family of fulleride polymers to the salts of multiply charged cations and thus opens a new direction in this field.     

Lattice dynamics of RbC60, RbC70 and phase transitions in A1C60: A neutron scattering study

1 C₆₀ (A = Rb, Cs, K) and RbC₇₀ have been investigated by neutron scattering. The studies include measurements in the high temperature rotator-, the polymer-, the dimer- and the low temperature isolator-phase and include investigations of the particular phase transitions. It is found that each of the phases can be characterized by specific features of its lattice dynamics which can be used for detailed studies of the dynamics of the rotator-polymer and the dimer-polymer transitions. Particular insight in the lattice dynamics is obtained from model calculations for the RbC₆₀ polymer and dimer phase. Received: 13 September 1996/Accepted: 11 November 1996     

Hydrothermal synthesis and structural characterization of (1−x)α-Fe2O3-xSnO2 nanoparticles

Structural and morphological characteristics of (1−x)α-Fe₂O₃-xSnO₂ (x=0.0-1.0) nanoparticles obtained under hydrothermal conditions have been investigated by X-ray diffraction (XRD), transmission Mössbauer spectroscopy, scanning and transmission electron microscopy as well as energy dispersive X-ray analysis. On the basis of the Rietveld structure refinements of the XRD spectra at low tin concentrations, it was found that Sn⁴⁺ ions partially substitute for Fe³⁺ at the octahedral sites and also occupy the interstitial octahedral sites which are vacant in α-Fe₂O₃ corundum structure. A phase separation of α-Fe₂O₃ and SnO₂ was observed for x≥0.4: the α-Fe₂O₃ structure containing tin decreases simultaneously with the increase of the SnO₂ phase containing substitutional iron ions. The mean particle dimension decreases from 70 to 6 nm, as the molar fraction x increases up to x=1.0. The estimated solubility limits in the nanoparticle system (1−x)α-Fe₂O₃-xSnO₂ synthesized under hydrothermal conditions are: x≤0.2 for Sn⁴⁺ in α-Fe₂O₃ and x≥0.7 for Fe³⁺ in SnO₂.     

Characterization of new-layered Cr(III)-doped chlorocadmiumphosphate, Cd(HPO4)Cl·[H3N(CH2)6NH3]0.5 crystal by EPR and optical studies

Cr(III)-doped Cd(HPO₄)Cl·[H₃N(CH₂)₆NH₃]_0.5, a new-layered cadmium phosphate, is synthesized in acidic condition at room temperature. EPR and optical studies are carried out at room temperature. Polycrystalline EPR spectrum reveals the presence of two sites of Cr(III) ions in this layered phosphate lattice with zero-field splitting values of 24.24 and 7.65 mT, indicating that Cr(III) ions are in distorted octahedral sites. The optical absorption spectrum of the sample indicates near octahedral symmetry for the dopant ions. Crystal field, inter-electronic and bonding parameters are evaluated by collaborating EPR and optical data. The evaluated parameters suggest the mode of entry of Cr(III) ion into the layered phosphate as interstitial site, and bonding between the metal and ligand is partially covalent.     

EPR, luminescence and IR studies of Mn activated ZnGa2O4 phosphor

Electron paramagnetic resonance (EPR), luminescence and infrared spectra of Mn²⁺ ions doped in zinc gallate (ZnGa₂O₄) powder phosphor have been studied. The EPR spectra have been recorded for zinc gallate phosphor doped with different concentrations of Mn²⁺ ions. The EPR spectra exhibit characteristic spectrum of Mn²⁺ ions (S=I=5/2) with a sextet hyperfine pattern, centered at g_eff=2.00. At higher concentrations of Mn²⁺ ions, the intensity of the resonance signals decreases. The number of spins participating in the resonance has been measured as a function of temperature and the activation energy (E_a) is calculated. The EPR spectra of ZnGa₂O₄: Mn²⁺ have been recorded at various temperatures. From the EPR data, the paramagnetic susceptibility (χ) at various temperatures, the Curie constant (C) and the Curie temperature (θ) have been evaluated. The emission spectrum of ZnGa₂O₄: Mn²⁺ (0.08 mol%) exhibits two bands centered at 468 and 502 nm. The band observed at 502 nm is attributed to ⁴T₁→⁶A₁ transition of Mn²⁺ ions. The band observed at 468 nm is attributed to the trap-state transitions. The excitation spectrum exhibits two bands centered at 228 and 280 nm. The strong band at 228 nm is attributed to host-lattice absorption and the weak band at 280 nm is attributed to the charge-transfer absorption or d⁵→d⁴s transition band. The observed bands in the FT-IR spectrum are assigned to the stretching vibrations of M-O groups at octahedral and tetrahedral sites.     

Temperature dependence of infrared and Raman modes in polymeric RbC60

Temperature dependence of the intra-molecular vibrational modes of C₆₀ in the quasi-1D polymeric RbC₆₀, across the low temperature transition at ∼50 K, has been probed through infrared (IR) and Raman spectroscopies. With the lowering of temperature, the split IR modes of RbC₆₀ are seen to harden but below 50 K a small but definitive signature of an anomalous softening is observed. In addition, the background IR transmission shows an increase below 50 K with the opening of a well defined gap in the electronic spectrum. The implications of these results, along with those of Raman measurements, are discussed in terms of the interaction of intra-molecular phonons with electrons and spin excitations in the system.     

Simulation of Al/Fe disorder in Ca2FexAl2−xO5

A method is described which is capable of simulating disorder across a range of composition. It is used to study the disorder of iron and aluminium on the octahedral and tetrahedral cation sites in the Brownmillerite phase Ca₂Fe_xAl_2−xO₅. The arrangements with the lowest lattice energies are those that maximize the number of Fe³⁺ on octahedral sites throughout the composition range. An exchange of one Fe³⁺ with one Al³⁺, which results in a decrease in the number of iron ions on octahedral sites, increases the lattice energy by an amount that is dependent on x but is independent of the number of exchanges. The exchange of trivalent cations also results in an expansion in the b lattice direction, accompanied by a decrease in the a and c directions across the full range of composition.     

Radiation induced paramagnetic centres in MgOAl2O3SiO2 glasses containing TiO2

Upon irradiation with ⁶⁰Co γ-rays Cordierite glasses with added TiO₂ display two dominant ESR resonances arising from (a) Ti³⁺ ions (b) holes trapped at non-bridging oxygen ions singly bonded to [SiO₄]^? tetrahedra. The Ti³⁺ ions appear to be in D_4h octahedral sites with the evident distributions between the principal g values arising from an isotropic randomness at the titanium sites. However, the g parameter distributions of the hole resonance, and their changes during the addition of TiO₂ indicate the development of Silicate structures in the glasses which are the precursors of the major low temperature crystalline phases. The invariance of the hole and electron resonance lines with pre-crystallization heat treatments indicates that neither the titanium associated structures or the basic silicate structure of the glass are changed by such treatments.     

Transferred hyperfine field of Rb2CoCl4 single crystals in the ferroelectric-incommensurate-normal phase by Rb NMR

The molecular susceptibility and paramagnetic shift of Rb₂CoCl₄ single crystals grown using the slow evaporation method were measured, and from these experimental results we obtained the transferred hyperfine interaction due to the transfer of spin density from Co²⁺ ions to Rb⁺ ions. The transferred hyperfine field was obtained for the ferroelectric, incommensurate, and normal phases. In the case of Rb(I), the transferred hyperfine interaction decreases with increasing temperature in the incommensurate phase, and increases with increasing temperature in the normal phase. The value of H_hf in the incommensurate and normal phases increases abruptly with increasing temperature in the case of Rb(II). These results indicate that the effects due to the transfer of spin density from Co²⁺ ions to the Rb(I) and Rb(II) ions are large above T_i. In particular, the effect due to the transfer of spin density to Rb(II) ions in the normal phase is very large; the variations with temperature of the transferred hyperfine interactions of the Rb(I) and Rb(II) nuclei are more or less continuous in T_c1 and T_i, and are not affected by the ferroelectric-incommensurate-normal phase transitions.     

Rb掺杂C60单晶的相衍变和电子态

在C₆₀单晶超高真空解理面上制备C₆₀的Rb填隙化合物薄膜.用同步辐射光电子能谱研究了相衍变过程.观察到对应于固溶相、Rb₁C₆₀和Rb₃C₆₀的电子态密度分布.当数纳米厚Rb₃C₆₀薄膜在C₆₀单晶（111）解理面形成后，室温条件下进一步沉积Rb至样品表面不产生fcc到bct或bcc结构相变.C_{60 关键词： 4}C₆₀和Rb₅C₆₀吸附相')" href="#">金属性Rb₄C₆₀和Rb₅C₆₀吸附相 60单晶')" href="#">C₆₀单晶 相衍变 同步辐射光电子能谱     

Electron spin resonance of diluted solid solutions of MnO2 in Y2O3

Electron spin resonance spectra of Mn²⁺ in diluted solid solutions of MnO₂ in Y₂O₃ have been studied at room temperature for Mn concentrations between 0.20 and 2.00 mol%. Isolated Mn²⁺ ions in sites with two different symmetries were observed, as well as Mn²⁺ ions coupled by the exchange interaction. The relative concentration of isolated to coupled Mn²⁺ ions decreases with increasing manganese concentration. The results are consistent with the assumption that the manganese ions occupy preferentially the C₂ symmetry sites. A theoretical calculation based on this model yields an effective range of the exchange interaction between Mn²⁺ ions of 0.53 nm, of the same order as that of Mn²⁺ ions in CaO.     

High-field electron paramagnetic resonance study of the polymerization in Na2Rb1−x Cs x C60

We report on the study of the magnetic properties of the low-temperature polymer phases in N₂Rb_1?xCs_xC₆₀ at 110 GHz microwave frequency withx varying between 0 and 1. The magnetic and structural properties of the polymer phase strongly depend on the Cs content and its electronic structure progressively becomes quasi-one-dimensional asx is increased. While the electronic properties of the polymeric Na₂RbC₆₀ appear to be close to three-dimensional metal, Na₂Rb_0.3Cs_0.7C₆₀ shows characteristics of quasi-one-dimensional metal where instability in the electronic structure was found as detected by the sudden disappearance of the ESR intensity due to the opening of the gap at the Fermi surface. The observation of an additional resonance line below 15 K, which could be attributed to antiferromagnetic resonance, suggests that the low-temperature polymeric phase in Na₂Rb_0.3Cs_0.7C₆₀ has a well-defined magnetic ground state.     

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.     

Magnetic contribution to heat capacity and entropy of nickel ferrite (NiFe2O4)

The heat capacity of nickel ferrite was measured as a function of temperature from 50 to 1200 °C using a differential scanning calorimeter. A thermal anomaly was observed at 584.9 °C, the expected Curie temperature, T_C. The observed behavior was interpreted by recognizing the sum of three contributions: (1) lattice (vibrational), (2) a spin wave (magnetic) component and (3) a λ-transition (antiferromagnetic-paramagnetic transition) at the Curie temperature. The first was modeled using vibrational frequencies derived from an experimentally-based IR absorption spectrum, while the second was modeled using a spin wave analysis that provided a T^3/2 dependency in the low-temperature limit, but incorporated an exchange interaction between cation spins in the octahedral and tetrahedral sites at elevated temperatures, as first suggested by Grimes [15]. The λ-transition was fitted to an Inden-type model which consisted of two truncated power law series in dimensionless temperature (T/T_C). Exponential equality (m=n=7) was observed below and above T_C, indicating symmetry about the Curie temperature. Application of the methodology to existing heat capacity data for other transition metal ferrites (AFe₂O₄, A=Fe, Co) revealed nearly the same exponential equality, i.e., m=n=5.     

C60薄膜的离子注入损伤研究

在200 keV重离子加速器上，用120—360 keV的H,N,Ar和Mo离子注入C₆₀薄膜．对注入后薄膜的拉曼谱进行了分析．结果表明，不同离子注入C₆₀薄膜后，C₆₀的1469 cm^-1特征峰随注入剂量的增加均呈指数式下降，同时在1300—1700 cm^-1范围出现非晶碳峰，并逐渐增强，最终完全非晶化．而且1469 cm^-1拉曼峰的强度及C₆₀薄膜完全非晶化所对应的剂量与注入离子的种类和能量有关．进一步的分析表明，C₆₀分子的损伤主要是由注入离子的核能量转移所造成，与电子能量转移无关．H离子注入C₆₀薄膜后，1469 cm^-1处特征拉曼峰向短波方向非对称展宽，这可能是注入的H离子通过电子能量转移使C₆₀分子发生聚合的结果. 关键词：     

Dust acoustic wave oscillations in C60 molecule

In this letter, dispersion properties of low-frequency electrostatic waves in a C₆₀ molecule are investigated. It is assumed that C₆₀ molecule is charged due to the field emission, and hence the C₆₀ molecule can be regarded as charged dust spheres surrounded by degenerate electrons and ions. We obtain the dispersion relation for the low-frequency electrostatic oscillations in the C₆₀ molecule by using the quantum hydrodynamic model in conjunction with the Poisson equation.     

Energy distributions of atomic and molecular ions sputtered by C60 projectiles

In the process of investigating the interaction of fullerene projectiles with adsorbed organic layers, we measured the kinetic energy distributions (KEDs) of fragment and parent ions sputtered from an overlayer of polystyrene (PS) oligomers cast on silver under 15 keV C₆₀⁺ bombardment. These measurements have been conducted using our TRIFT™ spectrometer, recently equipped with the C₆₀⁺ source developed by Ionoptika, Ltd. For atomic ions, the intensity corresponding to the high energy tail decreases in the following order: C⁺(E^−0.4) > H⁺(E^−1.5) > Ag⁺(E^−3.5). In particular, the distribution of Ag⁺ is not broader than those of Ag₂⁺ and Ag₃⁺ clusters, in sharp contrast with 15 keV Ga⁺ bombardment. On the other hand, molecular ions (fragments and parent-like species) exhibit a significantly wider distribution using C₆₀⁺ instead of Ga⁺ as primary ions. For instance, the KED of Ag-cationized PS oligomers resembles that of Ag⁺ and Ag_n⁺ clusters. A specific feature of fullerene projectiles is that they induce the direct desorption of positively charged oligomers, without the need of a cationizing metal atom. The energy spectrum of these PS⁺ ions is significantly narrower then that of Ag-cationized oligomers. For characteristic fragments of PS, such as C₇H₇⁺ and C₁₅H₁₃⁺ and polycyclic fragments, such as C₉H₇⁺ and C₁₄H₁₀⁺, the high energy decay is steep (E⁻⁴ − E⁻⁸). In addition, reorganized ions generally show more pronounced high energy tails than characteristic ions, similar to the case of monoatomic ion bombardment. This observation is consistent with the higher excitation energy needed for their formation. Finally, the fraction of hydrocarbon ions formed in the gas phase via unimolecular dissociation of larger species is slightly larger with gallium than with fullerene projectiles.