Preparation and Eh--pH diagrams of Fe(II)--Fe(III) green rust compounds; hyperfine interaction characteristics and stoichiometry of hydroxy-chloride, -sulphate and -carbonate

Fe(II)--Fe(III) hydroxy-chloride, -sulphate and -carbonate were prepared by oxidation of a ferrous hydroxide precipitate in anion-containing aqueous solutions. The compounds are characterized by monitoring the redox potential E_h and the pH of stochiometric suspension vs time with the appropriate concentration ratios. X-ray diffraction allows us to characterize the crystal structure by distinguishing “green rust one” (GR1) from “green rust two” (GR2). Since green rusts (GRs) are of a pyroaurite-sjögrenite-like structure, i.e., consisting of intercalated foreign anions and water molecules in the interlayers between the brucite-like layers of Fe(OH)₂, their chemical formulae can be determined from the Mössbauer spectra. Three quadrupole doublets are observed: D₁ and D₂ correspond to a ferrous state with isomershift IS of about 1.27 mm s^-1 and quadrupole splittings QS of about 2.85 and 2.60 mm s^-1, respectively, whereas D₃ corresponds to a ferric state with IS and QS of about 0.4 mm s^-1. The hyperfine parameters of these doublets are similar from one green rust to another but their intensity ratios vary considerably. Finally, E_h and pH equilibrium diagrams of the Fe species in the presence of chloride, sulphate and carbonate anions contained within the water solution are drawn and the thermodynamic conditions of existence and degrees of oxidation of green rusts are discussed.     

New derivatives of coumarin: 2-(N-R-imino)-2H-1-benzopyrans

Methods of synthesizing previously unknown derivatives of coumarin — 2-(N-R-imino)-2H-1-benzopyrans, where R = Alk, Ar — are proposed. Possibilities of alternative synthetic schemes are discussed, and hypotheses concerning probable mechanisms of the reactions are formulated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 760–766, June, 1994. Original article submitted May 23, 1994.     

The Assessment of Reservation Prices of an Intermediate R&D Result and Patent Reward Under Oligopolistic Competitive Behaviour

One of the shortcomings of R&D evaluation is a lack of emphasis on analytical assessment of the value of an on-going R&D project. This paper addresses the problem concerning the distributive aspect of access to superior knowledge. Decision tree analysis and probability models appear to be appropriate tools for assessing the values of an intermediate result and patent reward of a firm's R&D decision in an environment of perfect information and oligopolistic competition. The assessed values are used as minimum prices acceptable to the firm when the knowledge is disseminated to the public. This paper will attempt to resolve this problem through the determination of the appropriate values of the reservation price of the first-stage invention in terms of the final reward and of a patent reward for which the inventor is willing to apply.     

A branching process model for sand avalanches

An analytically solvable model for sand avalanches of noninteracting grains of sand, based on the Chapman-Kolmogorov equations, is presented. For a single avalanche, distributions of lifetimes, sizes of overflows and avalanches, and correlation functions are calculated. Some of these are exponentials, some are power laws. Spatially homogeneous distributions of avalanches are also studied. Computer simulations of avalanches of interacting grains of sand are compared to the solutions to the Chapman-Kolmogorov equations. We find that within the range of parameters explored in the simulation, the approximation of noninteracting grains of sand is a good one.     

XPS and XAES study of the interaction of palladium and copper overlayers with fullerene films

X-ray photoelectron and Auger spectroscopies were used to examine surface bonding and overlayer growth during palladium and copper deposition onto films of fullerene, C₆₀ The results were consistent with metal cluster formation on C₆₀. The observed positive core electron binding energy shifts in small metallic clusters supported on C₆₀ were shown to originate in metal-fullerene interaction accompanied by charge transfer. Palladium-fullerene intermixing at temperatures as low as ss 50°C was observed for small Pd coverages.     

Direct SCF structure optimization of large molecules on networks of workstations

A program to optimize the structure of large molecules at the Hartree–Fock level of theory running concurrently on a network of workstations is presented. Problems encountered in obtaining nearly optimal speedup and their solutions are discussed. A simple scheduling algorithm is presented that enables up to 99.5% of the code to run in parallel. © 1993 John Wiley & Sons, Inc.     

Spin-trapped hydroxyl free radicals studied at low field by Field-Cycled Dynamic Nuclear Polarization

The technique of Field-Cycled Dynamic Nuclear Polarization (FC-DNP) involves the EPR irradiation of a free radical solution and the subsequent observation of the NMR signal, the experiment being carried out at a range of magnetic field strengths in order to measure the free radical’s EPR spectrum. In this work FC-DNP has been used to study the EPR spectrum of DMPO spin-trapped hydroxyl free radicals at magnetic field strengths between 0.5 mT and 13.0 mT (5–130 Gauss). The low-field EPR spectrum contains six separate EPR lines, in contrast to the well-known X-band spectrum where only four are seen. Knowledge of the spin-adduct’s EPR spectrum will be of use to workers involved in low-field EPR, especially those conducting biological or in-vivo spin-trapping experiments.     

Systematics of flux jumps and the stabilizing effect of flux creep in a La1.86Sr0.14CuO4 single crystal

Flux jumps have been observed in a large (138 mg) single crystal of La_1.86Sr_0.14CuO₄. Both complete and incomplete flux jumps are observed with the energy dissipated by complete flux jumps consistent with temperature rises to nearly T_c. The systematics of these flux jumps with respect to field history, temperature and the time duration of the hysteresis measurements are reported. The field at which flux jumps first occur and their subsequent spacing are not consistent with a simple adiabatic theory of flux jumps for our experimental conditions. Instead, the crystal is observed to be stabilized against flux jumps by flux creep which occurs during the time interval over which field steps are accomplished as well as during imposed time intervals between field steps.     

Optical switching between bistable soliton states: a theoretical review

In this paper we summarize what is currently known about optical switching between bright bistable soliton states in one and higher dimensions. A guideline to selecting media with appropriate intensity-dependent refractive indices to support bistable solitary waves is presented. The stability criterion for robustness of the solitary waves is discussed. Finally, some methods and numerical examples of optical switching are presented.     

A Faster Deterministic Maximum Flow Algorithm

Cheriyan and Hagerup developed a randomized algorithm to compute the maximum flow in a graph with n nodes and m edges in O(mn + n² log²n) expected time. The randomization is used to efficiently play a certain combinatorial game that arises during the computation. We give a version of their algorithm where a general version of their game arises. Then we give a strategy for the game that yields a deterministic algorithm for computing the maximum flow in a directed graph with n nodes and m edges that runs in time O(mn(log_{m/n log n}n)). Our algorithm gives an O(mn) deterministic algorithm for all m/n = Ω(n^ε) for any positive constant ε, and is currently the fastest deterministic algorithm for computing maximum flow as long as m/n = ω(log n).