A Double Isotopic Labelling Study of the Infrared Spectra of the Linkage Isomers [Pd(bipy)(SCN)2], [Pd(bipy)(NCS)2] and Related Complexes

Abstract

The IR spectra of the linkage isomers [Pd(bipy)(SCN)₂] and [Pd(bipy)(NCS)₂] have been determined in the C≡N stretching region (2200–2000 cm^?1) and below 500 cm^?1. The band shifts resulting from deuteration of the 2,2′-bipyridine (bipy) ring and ¹⁵NCS-labelling are shown to provide a ready means for distinguishing between the internal ligand modes, the μPd-N(bipy) and μPd-SCN/μPd-NCS vibrations. The assignment technique has been further extended to the complexes [Pt(bipy)(SCN)₂] and [Pd(phen)(SCN)₂] (phen = 1,10-phenanthroline). Finally, a comparison between the IR spectra of [Pd(bipy)(NCO)₂], [Pd(bipy)(NCS)₂] and [Pd(bipy)(SCN)₂] reveals that the frequencies μM-NCO, μM-NCS and μM-SCN decrease in the sequence NCO > NCS > SCN.     

Linear Stability of the Elliptic Lagrangian Triangle Solutions in the Three-Body Problem

This paper concerns the linear stability of the well-known periodic orbits of Lagrange in the three-body problem. Given any three masses, there exists a family of periodic solutions for which each body is at the vertex of an equilateral triangle and travels along an elliptic Kepler orbit. Reductions are performed to derive equations which determine the linear stability of the periodic solutions. These equations depend on two parameters - the eccentricity e of the orbit and the mass parameter β=27(m₁m₂+m₁m₃+m₂m₃)/(m₁+m₂+m₃)². A combination of numerical and analytic methods is used to find the regions of stability in the βe-plane. In particular, using perturbation techniques it is rigorously proven that there are mass values where the truly elliptic orbits are linearly stable even though the circular orbits are not.     

Graphite powder and multiwalled carbon nanotubes chemically modified with 4-nitrobenzylamine.

We demonstrate that graphite powder and multiwalled carbon nanotubes (MWCNTs) can be derivatised by 4-nitrobenzylamine (4-NBA) simply by stirring the graphite powder or MWCNTs in a solution of acetonitrile containing 10 mM 4-NBA. We propose that 4-NBA partially intercalates at localised edge-plane or edge-plane-like defect sites and this hypothesis with a range of experimental data provided by electrochemistry in both aqueous and nonaqueous media, electron microscopy and X-ray powder diffraction.     

Regular orientable imbeddings of complete graphs

This paper classifies the regular imbeddings of the complete graphs K_n in orientable surfaces. Biggs showed that these exist if and only if n is a prime power p^e, his examples being Cayley maps based on the finite field F = GF(n). We show that these are the only examples, and that there are $\text{φ(n ? 1)}\text{e}$ isomorphism classes of such maps (where φ is Euler's function), each corresponding to a conjugacy class of primitive elements of F, or equivalently to an irreducible factor of the cyclotomic polynomial Φ_{n ? 1}(z) over GF(p). We show that these maps are all equivalent under Wilson's map-operations H_i, and we determined for which n they are reflexible or self-dual.     

The effect of casting solvent on the material properties of poly(γ-methyl-D-glutamate)

The effect of casting solvent on the material properties of poly(γ-methyl-D -glutamate), PMDG, was investigated. The specific solvents used were chloroform, trifluoroacetic acid, dichloroacetic acid, methylene chloride, hexafluoroisopropanol, and tetrachloroethane. The different nature of these solvents controlled the degree of α, β, or random coil contents of the final film. The effect of the morphology on material properties induced by the respective solvents was investigated by dynamic mechanical measurements of the dry films, stress strain behavior of both wet and dry films as well as by wide-angle x-ray diffraction, small-angle light scattering, and optical microscopy. Infrared spectroscopy was used to help determine α or β content. It was found that the casting solvent has considerable influence on material behavior and morphology. These differences are reflected in both the dynamical mechanical (small strain) and stress–strain (large strain) measurements as well as the x-ray scattering and optical microscopy. It was noted by light scattering that all films gave rise to anisotropic rod scattering with the exception of the β film cast from trifluoroacetic acid. This latter film appeared to be optically isotropic.     

Scattering of light from deformed regions surrounding voids and inclusions in high polymers

The H_v cloverleaf scattering pattern sometimes found for amorphous polymers can arise from the birefringent region caused by the strain surrounding a void or an inclusion in a polymer. The form of such a pattern may be theoretically explained by extension of a theory due to Goldstein.     

Wave coalescence and entrainment in vertical annular two-phase flow

A rigorous model for wave coalescence has been derived. The wave coalescence process has also been modelled by a Monte-Carlo technique. The results of the theories are in general in good agreement with the available experimental data. It had been noted that coalescence of two waves was accompanied by a large burst of entrainment. The above coalescence theory has been used to calculate that component of entrainment that is due to coalescence. Comparison of this and experimental data shows that the entrainment due to coalescence can be a significant portion of the total entrainment.     

Homolytic reactions of polyfluoroaromatic compounds. X. Biphenylyl radicals in the thermolysis of aroyl peroxides in polyfluoroaromatic solvents

The thermolyses of a number of aroyl peroxides in hexafluorobenzene, and of benzoyl peroxide in octafluorotoluene, gave the corresponding biaryls which were isolated by steam distillation. Mass spectrometry of the residues showed evidence of biphenylyl radicals arising from the arylation of the peroxides themselves or, possibly, of the derived aroic acids. Terphenyls, and the corresponding σ-intermediate radicals, could be found, and the relative molecular masses of the latter components showed that subsequent arylation of the main binuclear products was not the main source of terphenyls.