The oxidation of fullerenes (C<Subscript>60</Subscript>, C<Subscript>70</Subscript>) with various oxidants under ultrasonication

The reaction of C₆₀, under ultrasonication, with various oxidants, such as 3-chloroperoxy benzoic acid (Fluka 99%), 4-methyl morpholine N-oxide (Aldrich 97%), chromium (VI) oxide (Aldrich 99.9%), and the oxone® monopersulfate compound, causes the oxidation of fullerenes at room temperature. The FAB-MS spectra and HPLC profile confirmed that the products of fullerene oxidation were [C₆₀(O)_n] (n=1～3 or n=1). C₇₀ also reacted, under ultrasonication, with various oxidants, but the reaction rate of C₇₀ was lower than that of C₆₀.     

Cycloaddition of 2′-azidoethyl glycosides to fullerene[C60] under ultrasonic irradiation

The reactions of fullerene[C₆₀] with 2′-azidoethyl 2,3,4,6-tetra-O-acetyl-α-d-mannopyranoside (2a) and 2′-azidoethyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranoside (2b) under ultrasonic irradiation cause the cycloaddition of 2′-azidoethyl glycosides to fullerene[C₆₀] and lead to d-glycosyl fullerene[C₆₀] derivatives 3a and 3b, respectively. The glycosyl fullerene[C₆₀] derivatives were characterized by ¹H and ¹³C NMR, UV–vis, FAB-MS, FT-IR spectra and were a 1:1 glycoside fullerene [C₆₀]-adduct.     

CORAL: QSPR models for solubility of [C60] and [C70] fullerene derivatives

Quantitative structure–property relationships (QSPRs) between the molecular structure of [C₆₀] and [C₇₀] fullerene derivatives and their solubility in chlorobenzene (mg/mL) have been established by means of CORAL (CORrelations And Logic) freeware. The CORAL models are based on representation of the molecular structure by simplified molecular input line entry system (SMILES). Three random splits into the training and the external validation sets have been examined. The ranges of statistical characteristics of these models are as follows: n = 18, r ² = 0.748–0.815, s = 15.1 –17.5 (mg/mL), F = 47–71 (training set); n = 9, r ² = 0.806–0.936, s = 12.5–17.5 (mg/mL), F = 29–103 (validation set).     

The oxidation of fullerene [C70] with various oxidants by ultrasonication

The reaction of C₇₀ by ultrasonication with various oxidants such as 3-chloroperoxy benzoic acid (Fluka 99%), 4-methyl morpholine N-oxide (Aldrich 97%), chromium (VI) oxide (Aldrich 99.9%), and oxone^® monopersulfate compound, at room temperature causes the oxidation of fullerene [C₇₀(O)_n] (n=1–2 or n=1). The FAB-MS, UV–visible, FT-IR spectra, and HPLC analysis confirmed that products of fullerene oxidation are [C₇₀(O)_n] (n=1–2 or n=1).     

CNDO studies of Y-Ba-Cu-O superconductors V. Co/Cu substitution

Electronic properties of [Co _n Cu_3–n O₁₂]^–17 and [Ba₈Co _n Cu_3–n O₁₂]^–1 model clusters (n=0–3) are investigated using CNDO molecular orbital method. Our results well reproduce the trends of experimental data on Cu-O bond lengths and supposed negative charge transfer from central Cu(1)O chains to lateral Cu(2)O₂ planes with increasing Co content.     

Volume and grain boundary diffusion of implanted 113Sn in aluminium

Volume and grain boundary diffusion of ¹¹³Sn in aluminium was investigated with the radiotracer method. The implantation technique was used for tracer deposition to avoid problems of tracer hold-up caused by the oxide layer always present on aluminium. The diffusion penetration was chosen large enough to permit serial sectioning of samples with the aid of a microtome.The temperature dependence of the volume diffusivity was determined as D(T)=4.54×10^–5×exp[–(114.5±1.2)kJmol^–1/RT] m ² s ^–1. This confirms previous measurements from our group which already showed that Sn is the fastest foreign metal diffusor so far investigated in aluminium.Grain boundary diffusion of ¹¹³Sn in Al polycrystals was measured in the type-B kinetic regime. The grain boundary diffusion product P=sD _gb (s=segregation factor, =grain boundary width, D _gb=grain boundary diffusivity) was found to be strongly affected by the impurity content of aluminium. For Al polycrystals of 99.9992% nominal purity we obtained P _5N(T)=1.08×10^–8exp [–(96.9±7.5) kJ mol^–1/RT] m³ s^–1 and for less pure Al polycrystals of 99.99% nominal purity P _4N(T)=3.0×10^–10 exp [–(90.1±4.2) kJ mol^–1/RT] m³ s^–1 was determined. The grain boundary diffusion product in the purer material is more than one order of magnitude higher than in the less pure material. Very likely this is an effect of co-segregation of non-diffusant impurities into the grain boundaries.     

The substitution of Fe2+ ions by Ni2+ ions in green rust one compounds

The oxidation of Fe(OH)₂ in the presence of Cl^– or CO ₃ ^2– ions leads, in the first stage of the reaction, to chloride-containing green rust one (GR1), 3Fe(OH)₂· Fe(OH)₂Cl·nH₂O, or carbonate-containing GR1, 4Fe(OH)₂·Fe₂(OH)₄CO₃·nH₂O, respectively. These GR1 compounds give the ferric oxyhydroxides by further oxidation. If a hydroxide Ni _x Fe_1–x (OH)₂ is initially precipitated, the reaction leads to a nickelous-ferric compound isomorphous to the ferrous-ferric GR1, but stable with respect to the oxidizing action of air. Similarly, the oxidation of a nickelous-ferrous hydroxide, in the presence of excess OH^– ions, leads to a nickelous-ferric GR1, a layered hydroxide with anionic interlayers made of OH^– ions and water molecules. The Mössbauer spectra of these nickelousferric GR1 display two ferric doublets, D₀ withIS=0.34 mm/s andQS=0.45 mm/s and D₁ withIS=0.36 mm/s andQS=0.86 mm/s. The existence of a ferrous-ferric GR1 incorporating OH^– ions, a compound never observed so far, is strongly suspected.     

The oxidation of fullerene[C60] with various amine N-oxides under ultrasonic irradiation

The reaction of C60 with various amine N-oxides such as 3-picoline N-oxide (Aldrich 98.0%), pyridine N-oxide hydrate (Aldrich 95.0%), quinoline N-oxide (Aldrich 97.0%), isoquinoline N-oxide (Aldrich 98.0%) under ultrasonic irradiation in air at 25-43 degrees C causes the oxidation of fullerene[C60(O)n] (n=1-2 or n=1). The MALDI-TOF MS, UV-vis spectra, and HPLC profile confirmed that the products of fullerene oxidation are [C60(O)n] (n=1-2 or n=1).     

Central Limit Theorems for Nonlinear Hierarchical Sequences of Random Variables

Let a random variable x ₀ and a function f:[a, b] ^k [a, b] be given. A hierarchical sequence {x _n :n=0, 1, 2,...} of random variables is defined inductively by the relation x _n =f(x _{n–1, 1}, x _{n–1, 2}..., x _{n–1, k} ), where {x _{n–1, i} :i=1, 2,..., k} is a family of independent random variables with the same distribution as x _n–1. We prove a central limit theorem for this hierarchical sequence of random variables when a function f satisfies a certain averaging condition. As a corollary under a natural assumption we prove a central limit theorem for a suitably normalized sequence of conductivities of a random resistor network on a hierarchical lattice.     

CNDO studies of Y-Ba-Cu-O superconductors IV. The oxygen content effect

The dependence of the electronic structure of superconducting YBa₂Cu₃O _y , is investigated using a quasi-relativistic CNDO/1 molecular orbital method. Electronic structures of model clusters [Ba₈Cu₃O _n ] ^q with total chargesq=23–2n forn=11 to 14 in various Cu(1) coordination geometries are compared. The increasing oxygen content causes the electron density transfer from the central Cu(1)O(1,5) _x area to the lateral Cu(2)O(3,4)₂ sheets. The isomerization effects are important for the structures withn=12.     

结合除谱,差谱,二阶差谱的二氯化铜水溶液中直接接触离子对的紫外可见吸收光谱研究

The microstructure of aqueous CuCl₂ has been studied through lots of technologies for many years; however, it remains a controversial subject. In this study, a new spectroscopic method has been proposed to analyze the UV-visible spectra of thin film of CuCl₂/H₂O solutions at different concentrations. This method is the combination of ratio spectra, difference spectra and second order difference spectra. By using this method, two new bands at ~230 and ~380 nm are obviously observed. The bands are assigned as the contacted ion pairs[CuCl₃(H₂O)_n]^- or[CuCl₄(H₂O)_n]^2-, which demonstrates that ion pairs exist in the CuCl₂/H₂O solution. Such finding agrees with the recent theoretical spectra obtained by time-dependent density functional theory. Furthermore, the populations of the contacted ion pairs are discussed. This study not only offers the direct spectroscopic evidence of[CuCl₃(H₂O)_n]^- or[CuCl₄(H₂O)_n]^2- in aqueous CuCl₂, but also suggests that the spectroscopic analysis method is powerful to extract the weak bands in a strong overlapping spectrum.     

High-resolution infrared spectra of HCF3 in the ν6 (500 cm) and 2ν6 (1000 cm) regions: rovibrational analysis and accurate determination of the ground state constants C0 and DK

The high-resolution infrared spectrum of HCF₃ was studied in the ν₆ fundamental (near 500 cm⁻¹) and in the 2ν₆ overtones (near 1000 cm⁻¹) regions. The present study reports on the analysis of the hot bands in the ν₆ region, as well as the first observation and assignment of the 2ν₆² perpendicular band. Using ν₆, 2ν₆^±2–ν₆^±1 and 2ν₆² experimental wavenumbers, accurate coefficients C₀ and D_K⁰ of the K-dependent ground-state energy terms were obtained, using the so-called “loop method.” Ground-state energy differences Δ(K,J)=E₀(K,J)−E₀(K−3,J) were obtained for K=3–30. A least-squares fit of 81 such differences gave the following results (in cm⁻¹): C₀=0.1892550(15); D_K⁰=2.779(26) × 10⁻⁷.     

CNDO studies of Y-Ba-Cu-O superconductors II. Simple models of YBa2Cu3Ox

The electronic structure of YBa₂Cu₃O_x (x=6 and 7) is investigated using the CNDO molecular orbital method. Electronic structures of model clusters [Cu₃O₁₀]^–15, [Ba₈Cu₃O₁₀]⁺¹, [Y₈Cu₃O₁₀]⁺⁹ of the non-superconducting (x=6) and [Cu₃O₁₂]^–17, [Ba₈Cu₃O₁₂]^–1, [Y₈Cu₃O₁₂]⁺⁷ of the superconducting (x=7) phases are compared. Y and Ba layers cause a considerable electron density transfer from the central Cu(1) region.     

183Tungsten NMR studies

With a Fourier-transform spectrometer, especially developed for nuclei with weak NMR signals, the signal of¹⁸³W in a liquid diamagnetic sample was detected for the first time. The¹⁸³W Larmor frequencies and chemical shifts of WF₆, of [WO₄]^{– -} in aqueous solution, and of WCl₆ dissolved in CS₂ were determined with high accuracy. The¹⁸³W resonance is referred to that of the proton in H₂O and the magnetic moment of¹⁸³W in WF₆ isµ=0.116224 5 (7)µ _N. The scalar coupling constant in WF₆ was determined: |J(¹⁸³W–¹⁹F)|=(40.7±1.5) Hz; an upper limit for the coupling constant |J(¹⁸³W–¹⁷O)| in the [WO₄]^{– -} ion is given. The relaxation timesT ₁ andT ₂ of the¹⁸³W resonance in WF₆ were measured by steady state techniques.     

The tortuosity of occupied crossings of a box in critical percolation

We consider the length of an occupied crossing of a box of size [0,n]×[0, 3n] ^D–1 (in the short direction) in standard (Bernoulli) bond percolation on ^D at criticality. Let ¦s _n¦ be the length of the shortest such crossing. It is believed that ¦s _n¦ ^1+c in some sense for somec>0. Here we show that if the correlation length(p) satisfies (p)p _c}–p) ^– for some <1, then with a probability tending to 1, ¦s _n¦>/C ₁ n ^1/(logn)^–(1–)/. The assumption (p)C ₃(p _c–p)^– with <1 has been rigorously established^(1,2) for largeD, but cannot hold⁽³⁾ forD=2. In the latter case, let ¦l _n¦ be the length of the lowest occupied crossing of the square [0,n]². We outline a proof ofP _pc(¦l_n¦ n ^1+c)n ^– for somec, >0. We also obtain a result about the length of optimal paths in first-passage percolation.     

Thepin structure employed as current amplifier

Injection of excess carriers into thei region of a forward biasedpin diode diminishes proportionally its resistivity (primary circuit). Resistivity variations in thei region are used to control higher currents and powers in the secondary circuit. This basic idea is developed quantitatively for a simplified symmetrical model of thepin structure in a stationary regime and then generalized for the asymmetrical case. The frequency characteristics of the electronic device are studied. For demonstration of the theoretical results thepin structure in silicon with known parameters is used.Notation 2d [m] length ofi region - D [m² s^–1] ambipolar diffusion constant - e [C] electron charge - E ₂ [Vm^–1] electric field strength iny direction - i ₁ [Am^–2] current density inx direction - i ₂ [Am^–2] current density iny direction - i _m [Am^–2] current density due to recombination of carriers ini region - i _1ef ,i _2ef [Am^–2] effective values of currentsi ₁,i ₂ - i _ns ,i _ps [Am^–2] saturated current densities from the heavily dopedn, p regions - i intrinsic region - I [A] total current throughp-n junction - I ₁ [A] total current in pin diode - I ₂ [A] current in secondary circuit - k[J grad^–1] Boltzmann's constant - L=(D) [m] ambipolar diffusion length of carriers in middle region - n(x) [m^–3] excess electron concentration in middle region - ¯n [m^–3] average value of electron concentration in middle region - n _i [m^–3] intrinsic electron concentration - n _A [m^–3] acceptor concentration inp region - n _D [m^–3] donor concentration inn region - p(x) [m^–3] excess hole concentration in middle region - q [m²] area of electrodes 3 and 4 - Q [C] charge stored ini region - R [m^–3 s^–1] recombination rate - s [m] width of diode - t [m] thickness of diode - T [K] absolute temperature - U [V] voltage acrossp-n junction - U ₁ [V] voltage acrosspin diode - U ₂ [V] voltage across terminals of secondary circuit - U _m [V] voltage drop acrossi region - V _D [V] voltage drop acrossn — i andp — i junctions at zero load - W ₁ [W] power inpin diode circuit - W ₂ [W] power in secondary circuit - x [m] distance from center of diode - coefficient in current amplification factor - [rad] phase shift of diode current with respect to applied voltage - [s] life time of excess carriers ini region - [m² V^–1 s^–1] carrier mobility ini region in the symmetrical model - _n [m² V^–1 s^–1] electron mobility ini region - _p [m² V^–1 s^–1] hole mobility ini region - [^–1 m^–1] conductivity     

Optical absorption spectrum of Ni2+ ions doped in sodium potassium sulphate single crystal

Single crystals of nickel-doped sodium potassium sulphate were grown by slow evaporation method at room temperature. From the nature and position of the bands observed, a successful interpretation of all the observed bands could be made assuming the octahedral symmetry for the Ni^{2 +} ion in the crystal. The bands have been ascribed to transitions from the ground³A_2g(F) state to the excited³T_2g(F),¹E_g(D),³T_1g(F),¹T_2g(D) and³T_1g(P) states. The experimental and calculated energies are in good agreement. The crystal field parameters derived areDq= =880 cm^–1,B= 900cm^–1 andC=3600 cm^–1.One of the authors, Sujatha John expresses her thanks to the Secretary and the Principal, R. B. V. R. Reddy College, Hyderabad for according her permission to pursue the M. Phil. course.     

Temperature dependence of the indirect band gap, steepness parameter and related optical constants of [Kx(NH4)1−x]2ZnCl4 mixed crystals

Optical transmittance measurements near the absorption edge of [K_x(NH₄)_1−x]₂ZnCl₄ mixed crystals, where x=0.00, 0.232, 0.522, 0.644, 0.859 and 1.00, are reported over 276–350 K range. Analysis reveals that the type of transition is the indirect allowed one. The absorption edge shifted towards lower energy with increasing temperature. It is shown that [K_x(NH₄)_1−x]₂ZnCl₄ mixed crystals with x0.644 reveal a phase transition at 319 K, this phase disappeared at high concentrations of K⁺ ions. The steepness parameter is given, its value is used to estimate the temperature dependence of the indirect energy gap. In the region of the absorption edge, the absorption coefficient obeys Urbach's rule. Urbach parameters are investigated as a function of temperature.