Spectroscopic Evidence for Anionic Coordination Complexes of the Transition Metals with C70 and the Higher Fullerenes C76, C78, C82, C84, C86, C90, and C92

The carbonylate anions [M(CO)₅]^- (M = Mn, Re), [Co(CO)₄]^-, [CpFe(CO)₂]^-, and [CpM(CO)₃]^- (M = Mo, W) react with C₇₀ via single electron transfer processes to give, respectively, the corresponding 17-electron, metal-centered radicals Co(CO)₄, M(CO)₅ (M = Mn, Re), CpFe(CO)₂, and CpM(CO)₃ (M = Mo, W) in addition to the radical anion C₇₀^-. In secondary thermal or photochemical processes, the metal-centered radicals Co(CO)₄ and M(CO)₅ (M = Mn, Re) combine with the C₇₀^- to form the new η²-C₇₀ complexes [Co(CO)₃(η²-C₇₀)]^- and [M(CO)₄(η²-C₇₀)]^-. However, the metal-centered radicals CpM(CO)₃ (M = Mo, W) require photolysis to react with C₇₀^- to form [CpM(CO)₂(η²-C₇₀)]^-, whereas neither thermolysis nor photolysis induces reaction between CpFe(CO)₂ and C₇₀^-. The photochemical reaction of [Mn(CO)₅]^- with a mixture of higher fullerenes known to contain at least C₇₆, C₇₈, C₈₄, C₈₆, and C₉₀ resulted similarly in the formation of the higher fullerene complexes [Mn(CO)₄(η²-C_n)]^- (n = 76, 78, 80, 82, 84, 86, 88, 90, 92, 96, and 98), all identified using electrospray mass spectrometry.     

Evidence for η6 Coordination to a Fullerene

Evidence for the first η⁶ derivative of a fullerene, [MoC₆₀F₁₈(CO)₃] has been obtained from reaction between [Mo(CH₃CN)₃(CO)₃] and C₆₀F₁₈.     

Thaumasite––direct, woodfordite and other possible formation routes

Two main formation routes for thaumasite exist below 15 °C. One is the direct route from C–S–H reacting with appropriate carbonate, sulfate, Ca²⁺ ions and excess water. The other route is the woodfordite route from ettringite reacting with C–S–H, carbonate, Ca²⁺ ions and excess water, in which thaumasite arises through the intermediate formation of the solid solution woodfordite. The woodfordite route for thaumasite formation appears to be relatively quicker (although still slow) than the direct route, presumably because with the former the ettringite already has the octahedral [M(OH)₆] units that can facilitate the critical change from [Al(OH)₆]³⁻ to [Si(OH)₆]²⁻ groupings. Both routes are mutually dependent on each other. The presence of magnesium salts can modify the path to thaumasite formation. High pressure might be able to stabilise [Si(OH)₆]²⁻ groupings and allow thaumasite to become formed above 15 °C. This possibility is discussed.     

Ag glasses based on Zn-phosphate

The partial substitution of Zn²⁺ for Ag⁺ in Ag₄P₂O₇ leads to the formation of a wide glassy domain of composition [Ag₄P₂O₇] _(1−y) [Zn₂P₂O₇] _(y) with 0.20y0.87. The introduction of AgI in these materials results in a new series of glasses of formula [(Ag₄P₂O₇)_(1−y) (Zn₂P₂O₇)_(y)] _(1−X) [AgI] _(x), which domain for the composition y = 0.25 corresponds to 0x 0.64. The structure as well as the thermal and electrical properties of these materials are compared with those of the [AgPO₃] _(1−X) [AgI] _(x) and [Ag₄P₂O₇] _(1−x) [AgI] _(x) glasses.     

Biomimetic ion-channel sensors based on host-guest molecular recognition in Langmuir-Blodgett membrane assemblies

Biomimetic “ion-channel sensors” based on host-guest molecular recognition were constructed by incorporating several kinds of receptor molecules in Langmuir-Blodgett (LB) molecular assemblies deposited directly on glassy carbon electrodes. The receptors used were valinomycin, bis(crown ether)s, macrocyclic polyamine and cyclodextrin polyamine. The binding of charged stimulants (metal ions, inorganic and organic anions) to these receptors induced a marked increase (or decrease) in the ion permeability of the membranes, as detected by cyclic voltammetry using [Fe(CN)₆]^4- or [Ru(bpy)₃]²⁺ as marker ion. Such a mode of response, corresponding to model “channel opening (or closing)”, can be explained on the basis of the charge-charge interaction involving the stimulant, marker ion and lipid.     

Structure, nucleation and Eu luminescence in alkaline earth rare earth borate glass

In La₂O₃-MO-B₂O₃ ternary system, various glasses/ glass ceramics with M=Ca, Sr and Ba have been prepared. In this ternary system, homogeneous nucleation occuring in the B₂O₃ melt appears to be the cause for the formation of nanocrystallites, hence glass ceramics. The nucleation process is very much dependent on the alkaline earth used viz., with smaller alkaline earths like Ca, boron prefers (BO₄)⁵⁻ tetrahedral coordination with oxygen, while in the case of bigger alkaline earths like Ba and Sr, (BO₃)³⁻ triangular coordination seems to be predominant. Eu³⁺ in this glass system yields intense ⁵D₀→⁷F_j emission. A cursory view on the dependence of the various Judd-Ofelt parameters (Ω_k) indicates that Ω₂ parameter is very much dependent on the immediate vicinity of the luminescent ion (Eu³⁺) while Ω₄ is not. Various results based on these are discussed.     

Standing-wave solutions of the Enneper (sine-Gordon) equation

The present paper investigates the real solutions of the partial differential equations (∂²ω/∂u²) − (∂²ω/∂ν²) = sin ω (Enneper or sine-Gordon equation) that are of the FORM = F(|₁(u) · |₂(ν)). In the application of the Enneper equations to crystal physics such solutions may represent standing waves. A complete classification of these solutions and its degenerate cases is given.     

富集10B的Ce:Li6Lu(10BO3)3晶体生长及其闪烁性能

为了提高中子探测效率, 以富集¹⁰B的H₃¹⁰BO₃为原料, 通过提拉法生长了富集¹⁰B的Ce:Li₆Lu(¹⁰BO₃)₃晶体。X射线激发发射光谱测试表明: 其发光峰位于360~480 nm, 属于Ce³⁺离子典型的5d - 4f跃迁发光, 其闪烁发光效率为BGO晶体的3.9倍。在350 nm紫外光和¹³⁷Cs所发出的662 keV的γ射线激发下测得的衰减时间分别为21.0 ns 和31.7 ns, 在¹³⁷Cs辐射源激发下所测得的相对光输出是CsI(Tl)晶体的20%, 能量分辨率为9.7%。在慢化²⁵²Cf中子源激发下可以观测到明显的中子全能峰, 其能量分辨率为33%。上述研究结果表明, Ce:Li₆Lu(¹⁰BO₃)₃晶体具有较高的闪烁效率、快的衰减时间和良好的中子探测效率, 是一种具有应用前景的中子探测用闪烁晶体。     

ISOLATION AND CHARACTERISATION OF C60(CF3)2

From the products of reactions of [60]fullerene with either K₂PtF₆ at 470 °C or AgF at 520 °C, we have isolated C₆₀(CF₃)₂, the simplest trifluoromethylfullerene, which gives a single ¹⁹F NMR line at -69.5 ppm. The HPLC retention time is less than that of C₆₀F₂ confirming the trend observed for other fluoro- vs. trifluoromethylfullerenes namely that the latter elute more rapidly. Other trifluoromethyl- containing species, C₆₀(CF₃)₄O, C₆₀F₅CF₃, C₆₀(CF₃)₄H₂, C₆₀(CF₃)₆H₂, and C₆₀(CF₃H)₃ were detected in the product mixture.     

Experimental determination of the gyromagnetic ratio of thehelium-4 atom in terms of that of the helium-3 nucleus

The ratio R=γ_4He(2³S₁)/γ_3He (1¹S₀) has been measured using gaseous samples in low magnetic field. The result, R=864.02276±3×10 ^-8, leads to a value of γ_4He=1760.78798(3×10^-7)×10⁸ ×rad×s^-1×T^-1     

Synthesis and the luminescent properties of europium-activated Ca2SnO4 phosphors

The synthesis and photoluminescent (PL) properties of calcium stannate crystals doped with europium grown by mechanically activated in a high energy vibro-mill have been investigated. The characteristics of Ca₂SnO₄:Eu³⁺ phosphors were found to depend on the amounts of europium ions. The XRD profiles revealed that the system, (Ca_1−xEu_x)₂SnO₄, could form stable solid solutions in the composition range of x = 0–7% after being calcined at 1200 °C. The calcined powders emit bright red luminescence centered at 618 nm due to ⁵D₀ → ⁷F₂ electric dipole transition. Both XRD data and the emission ratio of (⁵D₀ → ⁷F₂)/(⁵D₀ → ⁷F₁) reveal that the site symmetry of Eu³⁺ ions decreases with increasing doping concentration. The maximum PL intensity has been obtained for 7 mol% concentration of Eu³⁺ in Ca₂SnO₄.     

Crystal structure and spectroscopic studies of NaGd(PO3)4

Single crystals of gadolinium–sodium polyphosphate NaGd(PO₃)₄ were grown for the first time using a flux method and characterized by X-ray diffraction. This phosphate crystallizes in a monoclinic system with P2₁/n space group and with the following unit-cell dimensions: a = 9.767(3) Å, b = 13.017(1) Å, c = 7.160(2) Å, β = 90.564(5)°, V = 910.3(4) Å³ and Z = 4. The crystal structure was solved from 3451 X-ray independent reflections with final R(F²) = 0.0219 and R_w(F²) = 0.056 refined with 164 parameters (). The atomic arrangement can be described as a long chain polyphosphate organization. Two infinite (PO₃)∝ chains with a period of eight tetrahedra run along the [0 1 1] direction. The structure of NaGd(PO₃)₄ consists of GdO₈ polyhedra sharing oxygen atoms with phosphoric group PO₄. Each Na⁺ ion is bonded to eight oxygen atoms.     

Rietveld refinement and spectroscopic studies of sodium lead fluoroapatite lacunaire synthesized by hydrothermal method

The structure of NaPb₉(PO₄)₆F(H₂O)_0.33, isostructural with apatite, was determined by X-ray powder diffraction methods and the result of Rietveld refinement is P6₃/m, a = 9.76396(8) Å and c = 7.27520(9) Å. The final refinement led to R_F = 5.4%, R_B = 6.6%. In the tunnel, the water molecule (O_w) and F⁻ ions appear to be located in 2b and 4e sites, with occupancies of 0.028(6) and 0.075(8), respectively. In the M(1) and M(2) sites the occupancies of Pb and Na are 0.282(3)/0.051(3) and 0.467(5)/0.033(5), respectively. The formula assigned to the compound is [Pb_3.38(4)Na_0.62(4)](1)[Pb_5.60(6)Na_0.40(6)](2)(PO₄)₆F_0.90(10)(H₂O)_0.33(7)□_0.77(17), where □ = vacancy. The assignment of the observed frequencies in the Raman and infrared spectra is discussed on the basis of a unit-cell group analysis and by comparison with fluor and chloroapatite analogs. The result of ³¹P and ²³Na magic angle spinning-nuclear magnetic resonance (MAS-NMR) spectroscopies confirmed the structural results.     

On the structure of the NiO–Al2O3 systems, studied by diffuse-reflectance spectroscopy

Diffuse-reflectance spectra of the NiO–Al₂O₃ systems in the 350–800 nm spectral domain are analysed. Two types of Ni²⁺complexes in γ-Al₂O₃ have been found at low concentrations (<5%): [Ni²⁺6O²⁻] and [Ni²⁺4O²⁻] with octahedral (O_h) and tetrahedral (T_d) symmetries, respectively. Coexistence of these two complexes is discussed in connection with the sample preparation and their thermal treatment.     

Elastic stiffness and thermal expansion coefficients of various refractory silicides and silicon nitride films

The elestic stiffness parameter E_f/(1−ν_f) and the thermal expansion coefficient _f were obtained for four different silicides (TiSi₂, TaSi₂, MoSi₂ and WSi₂) and for two different nitrides (chemically vapor-deposited Nitrox Si₃N₄ and r.f. plasma SiN) from stress-temperature measurements on identical films deposited on two different substrate materials. The values determined for _f and E_f/(1−ν_f) were quite similar for all silicides and averaged 15 ppm °C⁻¹ and 1.1 × 10¹² dyncm⁻² respectively. The thermal mismatch of these silicides is such that, once safely formed, the silicide film should be able to withstand high temperature processing steps without cracking. For the nitrides the values were essentially the same (approximately 1.5 ppm°C^-1), although the larger value of E_f/(1−ν_f) chemically vapor-deposited Si₃N₄ film (3.7 × 10¹² as opposed to 1.1 × 10¹² dyn cm^-2) indicates that it is somewhat stiffer than the SiN film.     

Stress relaxation in the interface between creep particle and elastic matrix-strengthening mechanism

The effect of a power law creep particle on interface behavior between the particle and elastic matrix is investigated by stress analysis. Using the results obtained through the stress analysis, the forces due to interaction of an applied stress and stress concentration with an edge dislocation are determined. The direct interaction between the edge dislocation and the creeping particle is studied under fully relaxed stress conditions. Through the investigation the following results are derived. Stress relaxation in the interface can be caused by power law creep along or by diffusion, or a combination of both mechanisms. The degree of stress relaxation caused by diffusion can be defined in terms of the relaxation time for both boundary diffusion and volume diffusion. The amount of stress relaxation caused by the power law creep particle is characterized by the quantity ₂ which is a function of Γ₀ = 2(1/√3)^{1 + m} × (σ_∞/2μ)^m(σ₀/σ_∞t^m), where m is strain rate hardening exponent, σ_∞ is applied stress, μ is the shear modulus, σ₀ is the material constant of the power law creep particle, and t is elapsed time. The value ₂ = 1.0 corresponds to the fully relaxed condition and ₂ = −0.6 corresponds to the initial state. The time to reach a fully relaxed condition is very sensitive to the strain rate exponent, with the smaller m values leading to longer times. The stress state of complete relaxation in the elastic matrix is equivalent to the solution of a void in an elastic matrix superposed on the solution of positive surface traction on the void. This result is identical to that obtained by Srolovitz et al. [Acta. Metall.32, 1979 (1984)]. When the stress is completely relaxed in the particle, all stress components (σ_r, σ_θand σ_rθ) are relaxed, while in the matrix relaxations are observed only for σ_rand σ_θ. The critical resolved shear stress and critical stress to climb the dislocation in the neighborhood of the particle exceed the Orowan stress. Also, the particle attracts the dislocation. Therefore the strengthening of a power law creep particle in an elastic matrix is caused by the Orowan mechanism and by attraction of the dislocation.     

Ultra intense glass laser system and laser–plasma interactions

The 30 TW GEKKO MII short pulse laser (25 J in 0.71 ps at 1 μm) is completed and is used for fast ignitor and particle accelerator research. The photon pressure of the laser at 10¹⁷-10¹⁸ W/cm² pushed the critical and quarter critical density plasmas forward, resulting in the strong red shifts of the second (2ω₀) and three-halves (3ω₀/2) harmonic emissions backscattered from CH or CD planes. A few hundred keV proton and deuteron emissions are also observed from CD planes.     

Optical properties, fluorescence mechanisms and energy transfer in Tm, Ho and Tm -Ho doped near-infrared laser glasses, sensitized by Yb

The optical properties of the rare elements Tm³⁺, Ho³⁺ and Yb³⁺ were systematically investigated in various glasses. The Tm³⁺ doped aluminozircofluoride glass shows higher quantum efficiency, longer lifetime and stronger fluorescence intensity than Tm³⁺ doped YSGG crystal and other Tm³⁺ doped glasses for the ³H₄ → ³H₆ transition. Similar quantum efficiency, longer lifetime and stronger fluorescence intensity were also found in Ho³⁺ doped aluminozircofluoride glass for the ⁵I₇ → ⁵I₈ transition. The higher quantum efficiencies of Tm³⁺ and Ho³⁺ in aluminozircofluoride glass are due to the longer lifetime and the lower phonon energy. The fluorescence mechanisms and energy transfer in the Yb³⁺ -Tm³⁺ system, Yb³⁺ -Ho³⁺ system and Yb³⁺ - Tm³⁺ -Ho³⁺ system were studied. The very strong fluorescence intensities in the Yb³⁺ -Tm³⁺ system for Tm³⁺ and the Yb³⁺ -Tm³⁺ -Ho³⁺ system for Ho³⁺ which are 1.68 times that of Tm³⁺ doped YSGG crystal and 2.25 times that of Tm³⁺---Ho³⁺ codoped YSGG crystal are attributed to the efficient Yb³⁺ → Tm³⁺, Yb³⁺ → Ho³⁺ and Tm³⁺ → Ho³⁺ energy transfer processes. The fluorescence processes are described by cross relaxations of ²F_5/2 → ³H₅ → ³H₄ → ³H₆ → ²F_7/2 and²F_5/2 → ³H₅ (or ²F_5/2 → ⁵I₆ → ³H₅) → ³H₄ → ⁵I₇ → ⁵I₈ → ³H₆ → ²F_7/2.     

Effects of spacer-chain length on the photoelectrochemical responses of monolayer assemblies with ruthenium tris(2,2′-bipyridine) - viologen linked disulfides

Photochemical and photoelectrochemical properties of ruthenium tris(2,2′-bipyridine) (Ru²⁺)-viologen (V²⁺) linked disulfides [RuCnVC₆S]₂ (n (number of methylene groups)=3, 7) with different spacer-chain lengths and Ru²⁺ disulfides [RuC_mS]₂ (m=13, 17) were compared. The luminescence intensity in CH₃CN was in the order of [RuC₁₃S]₂≈[RuC₁₇S]₂>[RuC₇VC₆S]₂[RuC₃VC₆S]₂, implying efficient photoinduced electron-transfer between Ru²⁺ and V²⁺ moieties in the linked compounds. The monolayer assembly of the compound was fabricated on a gold surface. In the presence of triethanolamine, the anodic photocurrent was clearly observed from the RuC_nVC₆S/Au (n=3, 7) electrode (gold electrode modified with [RuCnVC₆S]₂), and its intensity was substantially larger for n=7 than for n=3. Photocurrent action spectra for the RuC_nVC₆S/Au (n=3, 7) electrodes were well correlated with the corresponding electronic absorption spectra in solution. The photocurrent from the RuC₇VC₆S/Au electrode was reduced more effectively by the coexistence of a water-soluble viologen as compared with the RuC₃VC₆S/Au electrode. The photocurrent from the RuC_mS/Au (m=13, 17) electrode was very small. The results suggest that the spacer-chain length between the Ru²⁺ and the V²⁺ moieties profoundly affects the Ru²⁺-sensitized photocurrent.     

杂化钙钛矿(HOC2H4NH3)2CuCl4的制备与表征

采用低温溶液法合成了新型层状有序的含有羟基的有机/无机杂化钙钛矿材料(HOC₂H₄NH₃)₂CuCl₄, 采用元素分析、红外光谱、紫外-可见光吸收光谱、X射线衍射和X射线吸收精细结构等手段对其结构与性能进行了表征。结果表明:该材料通过无机框架诱导有机组分有序排列, 形成了规则的层状结构, 有序性高。该杂化钙钛矿材料的分解温度为212℃, 电阻率为2.86×10⁶ Ω·cm, 比不含羟基杂化钙钛矿的电阻率低两个数量级。紫外-可见光吸收光谱显示285 nm左右有一归因于电子从Cl(3p)价带顶跃迁到Cu(4s)导带底而产生的吸收峰。X射线吸收精细结构谱图表明: 二维层状杂化钙钛矿晶体中的Cu²⁺与6个Cl^-形成八面体配位, Cu-Cl键长为0.191 nm, 层间距为1.099 nm。