Mössbauer and infrared spectroscopic studies of novel mixed valence states in cobaltous ferrocyanides and ferricyanides

Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co⁺²Fe^II) and ferricyanides (Co⁺²Fe^III) in an ozone flow. The CN stretching bands occur at 2085 cm^–1 for Co⁺²Fe^II and at 2160 cm^–1 for Co⁺²Fe^III. After the ozonization process of Co⁺²Fe^II, an intense band approximately at 2125 cm^–1 is detected. This intermediate band must correspond to a mixed valence state of the type: Fe^II–CN–Co²⁺–NC–Fe^III Mössbauer spectra recorded in situ during the ozonization of Co⁺²Fe^II show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co⁺²Fe^II after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.     

A trajectory-following method for unconstrained optimization

A trajectory-following method with interesting properties is considered for solving unconstrained nonlinear programming problems. The trajectory is defined by a special system of ordinary differential equations. This system uses only the gradient of the objective function. Numerical examples are given.The work of the second author was supported by the DFG Schwerpunkt Anwendungs-bezogene Optimierung and Steuerung.     

Branched polymers in a wedge geometry in three dimensions

We investigate the statistical and dimensional properties of uniform star polymers attached by the branching vertex of degreef in a wedge geometry in three dimensions and described by the wedge angles and. We show that the growth constant is equal to ^f , where is the self-avoiding walk limit. Thef and (, ) dependences of the corresponding critical exponent _f (, ) are studied using Monte Carlo techniques. In the casef=1, our results are compared with existing predictions obtained from series expansion and renormalization group methods. We have also estimated the amplitudes for the mean square radius of gyration and the mean square end-to-end branch length. Our results for the ratio of the mean square radius of gyration of anf-star to that of a linear polymer of the same degree of polymerization attached in a similar wedge, and the analogous ratio for the mean square end-to-end branch length, are consistent with these ratios being lattice-independent quantities.     

Crystal structure and vibrational spectra of hydrazinium (2+) tri-μ-fluoro bis[pentafluorozirconate (IV)] fluoride and vibrational spectra of its hafnium analogue

Monoclinic (N₂H₆)₃Zr₂F₁₃·F crystallizes in space group P2₁-C ₂ ² (No. 4) with unit cell dimensionsa=5.670(1),b=10.984(2),c=10.601(2) Å,=93.88(1)°,V=658.7(4) ų andZ=2. Two different types of N₂H₆ ²⁺ ions are present. One is involved in strong H-bonds to F^– ions in infinite chains running along the a axis (the shortest N-F distance is 2.437(5) Å), and the other links the structure through weaker bi- and trifurcated H-bonds to fluorine ligands of the Zr₂F₁₃ ^5– ions. The N-N bond lengths range from 1.430(5) to 1.446(5) Å with apparently no meaningful correlation to the type of N₂H₂ ²⁺ ions. The Zr₂F₁₃ ^5– ions have very nearly C₂ point symmetry and are formed by joining two distorted bicapped trigonal prisms of ZrF₈-units through a common face. Distances of Zr-F terminal bonds range from 2.015(2) to 2.112(2) Å and of bridging bonds from 2.133(2) to 2.212(2) Å. (N₂H₆)₃Hf₂F₁₃·F is isomorphous. The vibrational spectra of the two compounds are nearly identical, with the exception of a strong infrared band, which is assigned to a stretching mode with the moving central atom within the anion. The anion part of the spectrum is simple, showing broad unresolved bands. The cation part shows two types of N₂H₆ ^– ions. H-Bonding is strongly present in the spectra, but no simple correlations with the H-bond strength is evident.     

Crystal and molecular structure of crenatine carbonate

The crystal and molecular structure of 1-ethyl-4-methoxy-9H-pyrido[3,4b]indole (crenatine) carbonate C₁₄H₁₄N₂O·H₂CO₃, (MS, m/z 226)M _R 288.3, a-carboline alkaloid, has been determined from X-ray diffraction data. The compound crystallizes in the space group Pbca with cell parameters:a=11.616(4),b=18.450(8),c=12.992(5)Å,V=2784(2)ų,Z=8,D _calc=1.375 g cm^–3, (MoK)=0.71069Å,(Mo K)=0.94 cm^–1,F(000)=1216,R/R _w =8.2/10.3% for 1099 reflections. The ring system of the-carboline nucleus is planar. The title compound shows a two center hydrogen bond between the indole N-H group and the oxygen atom of a carbonate group. The structure does not display hydrogen bonding between-carboline groups but rather a bonding network involving the carbonate group.     

The Binet-Pexider functional equation for rectangular matrices

IfK is a field of characteristic 0 then the following is shown. Iff, g, h: M _n (K) K are non-constant solutions of the Binet—Pexider functional equation

Stable in situ sorting and minimum data movement

In this paper, we describe an algorithm to stably sort an array ofn elements using only a linear number of data movements and constant extra space, albeit in quadratic time. It was not known previously whether such an algorithm existed. When the input contains only a constant number of distinct values, we present a sequence ofin situ stable sorting algorithms makingO(n lg^(k+1) n+kn) comparisons (lg^(K) means lg iteratedk times and lg* the number of times the logarithm must be taken to give a result 0) andO(kn) data movements for any fixed valuek, culminating in one that makesO(n lg*n) comparisons and data movements. Stable versions of quicksort follow from these algorithms.Research supported by Natural Sciences and Engineering Research Council of Canada grant No.A-8237 and the Information Technology Research Centre of Ontario.Supported in part by a Research Initiation Grant from the Virginia Engineering Foundation.     

Two-dimensional exponential model of the Euclidean field theory

It is proved that the two-dimensional exponential model of the field theory is trivial for ² > 8.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 42, No. 4, pp. 469–477, April, 1990.     

Impulse systems with fixed moments of shocks of general position: The structure of the set of moments of the shocks

Ordinary differential equations with impulse action are considered at fixed moments of time when finite limits points are admitted to the set of moments of the shocks. The topological structure of this set is clarified: it must be resolvable, in particular nowhere dense in R.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 42, No. 3, pp. 378–383, March, 1990.     

A certain periodic control problem for differential equations with impulses in the space of bounded numerical sequences

One considers the differential equation dx/dt=f(t, x) with the impulse action ¦_t=t_i=H_i(t_i,x) in the space of bounded numerical sequences, where f(t, x), H_i(t, x) are T-periodic, countable-dimensional vector-valued functions, is a positive parameter. One gives conditions for the existence of a control (₁,₂) such that the solution of the equation dx/dt=f(t, x)–₁ with impulse action x¦_t=t_i=H_i(t_i,x)–₂ assuming for t= the value x=x₀, be T-periodic.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 42, No. 2, pp. 271–275, February, 1990.