The search for organically bonded iron in New Zealand brown coals

Brown coal from two areas in New Zealand was treated with acids (HF and HCl) to remove the clays. Iron was then introduced into the “cleaned” coal by ion exchange. Mössbauer spectra of the untreated coal, the low temperature ash of the coal, “cleaned” coal and ion-exchanged coal were analysed. From these spectra we conclude that a pair of lines with QS～1 mm s^?1 and IS～0.45 mm s^?1 is probably due to organically bonded iron.     

Determination of absolute configuration using density functional theory calculation of optical rotation: chiral alkanes

The recently developed Gauge-Invariant (Including) Atomic Orbital (GIAO) based Time-Dependent Density Functional Theory (TDDFT) methodology for the calculation of transparent spectral region optical rotations of chiral molecules provides a new approach to the determination of absolute configurations. Here, we discuss the application of the TDDFT/GIAO methodology to chiral alkanes. We report B3LYP/aug-cc-pVDZ calculations of the specific rotations of the 22 chiral alkanes, 2-23, of well-established Absolute Configuration. The average absolute deviation of calculated and experimental [alpha](D) values for molecules 2-22 is 24.8. In two of the molecules 2-23, trans-pinane, 10, and endo-isocamphane, 13, the sign of [alpha](D) is incorrectly predicted. Our results demonstrate that absolute configurations of alkanes can be reliably assigned by using B3LYP/aug-cc-pVDZ TDDFT/GIAO calculations if, but only if, [alpha](D) is significantly greater than 25. In the case of (-)-anti-trans-anti-trans-anti-trans-perhydrotriphenylene, 1, [alpha](D) is -93 and TDDFT/GIAO calculations reliably lead to the absolute configuration R(-).     

Second-order relativistic electron capture

Starting with the impulse approximation, we analyse second-order effects in relativistic electron capture. The relation of this model with relativistic distorted-wave approximations is clarified. In particular it is shown that the second-order spin-coupling terms in the RCDW theory are consistent with the correct form given by perturbation theory. In the semirelativistic limit, the RCDW results are shown to accord with the formulae of Moiseiwitsch for flip and nonflip transitions in the ultra-relativistic limit. This confirms that the continuum-distorted-wave model generalises to relativistic spinors, and highlights the defects of scalar models. We also present a new symmetric eikonal theory which gives reliable results for capture without change of spin, but leads to a divergent total cross section for spin-flip transitions in the second-order term. This effect, which is quite distinct from the spurious spin-flip amplitudes of the scalar symmetric eikonal theory, is taken as further evidence that the eikonal approximation is not valid for magnetic transitions.     

A TEMPO-catalyzed oxidation–reduction method to probe surface and anhydrous crystalline-core domains of cellulose microfibril bundles

Cellulose - A modified TEMPO-catalyzed oxidation of the solvent-exposed glucosyl units of cellulose to uronic acids, followed by carboxyl reduction with NaBD4 to 6-deutero- and...     

Sharp decay rates for the fastest conservative diffusions

In many diffusive settings, initial disturbances will gradually disappear and all but their crudest features — such as size and location — will eventually be forgotten. Quantifying the rate at which this information is lost is sometimes a question of central interest. Here this rate is addressed for the fastest conservative nonlinearities in the singular diffusion equation

$u_t=\mathrm{\Delta }(u^m),{(n?2)}_{+}/n<m?n/(n+2),u,t?0,\mathbf{x}\in {\mathbf{R}}^n,$

which governs the decay of any integrable, compactly supported initial density towards a characteristically spreading self-similar profile. A potential theoretic comparison technique is outlined below which establishes the sharp $1/t$ conjectured power law rate of decay uniformly in relative error, and in weaker norms such as $L^1({\mathbf{R}}^n)$. To cite this article: Y.J. Kim, R.J. McCann, C. R. Acad. Sci. Paris, Ser. I 341 (2005).     

A discrete time-dependent method for metastable atoms and molecules in intense fields

The full-dimensional time-dependent Schr?dinger equation for the electronic dynamics of single-electron systems in intense external fields is solved directly using a discrete method. Our approach combines the finite-difference and Lagrange mesh methods. The method is applied to calculate the quasienergies and ionization probabilities of atomic and molecular systems in intense static and dynamic electric fields. The gauge invariance and accuracy of the method is established. Applications to multiphoton ionization of positronium, the hydrogen atom and the hydrogen molecular ion are presented. At very high laser intensity, above the saturation threshold, we extend the method using a scaling technique to estimate the quasienergies of metastable states of the hydrogen molecular ion. The results are in good agreement with recent experiments.     

C-terminal processing of yeast Spt7 occurs in the absence of functional SAGA complex

Background  

Spt7 is an integral component of the multi-subunit SAGA complex that is required for the expression of ~10% of yeast genes. Two forms of Spt7 have been identified, the second of which is truncated at its C-terminus and found in the SAGA-like (SLIK) complex.     

Fast Diffusion to Self-Similarity: Complete Spectrum,Long-Time Asymptotics,and Numerology

The complete spectrum is determined for the operator on the Sobolev space W^1,2(Rⁿ) formed by closing the smooth functions of compact support with respect to the norm Here the Barenblatt profile is the stationary attractor of the rescaled diffusion equation in the fast, supercritical regime m the same diffusion dynamics represent the steepest descent down an entropy E(u) on probability measures with respect to the Wasserstein distance d₂. Formally, the operator H=HessE is the Hessian of this entropy at its minimum , so the spectral gap H:=2–n(1–m) found below suggests the sharp rate of asymptotic convergence: from any centered initial data 0u(0,x)L¹(Rⁿ) with second moments. This bound improves various results in the literature, and suggests the conjecture that the self-similar solution u(t,x)=R(t)^–n(x/R(t)) is always slowest to converge. The higher eigenfunctions – which are polynomials with hypergeometric radial parts – and the presence of continuous spectrum yield additional insight into the relations between symmetries of Rⁿ and the flow. Thus the rate of convergence can be improved if we are willing to replace the distance to with the distance to its nearest mass-preserving dilation (or still better, affine image). The strange numerology of the spectrum is explained in terms of the number of moments of .Dedicated to Elliott H. Lieb on the occasion of his 70th birthday.     

A 57Fe Mössbauer study of four pyrite compounds: CoS2, NiS2, CoSe2 and NiSe2

Mössbauer spectra of ⁵⁷Fe-doped CoS₂, NiS₂, CoSe₂ and NiSe₂ have been taken at various temperatures between 300 and 16 K, and the hyperfine parameters H and θ measured for those substances showing magnetic hyperfine splitting. Quadrupole splitting $\text{QS}\text{(=}\text{1}\text{2}\text{e}{}^2\text{qQ)}$ was also measured and for NiS₂ and CoS₂ the sign of QS was determined.The room temperature value of QS showed a similar behaviour in the series FeS₂CoS₂NiS₂ to that in the series FeSe₂CoSe₂NiSe₂. The absolute value of QS decreased slightly below the magnetic transition temperature in those compounds which showed magnetic ordering.