Monomeric, dimeric and hexameric resorcin[4]arene assemblies with alcohols in apolar solvents

Resorcin[4]arenes in an apolar solvent containing alcohols exist in three forms of self-assembled aggregates which have been characterised by the technique of diffusion NMR spectroscopy.     

On the spectroscopic and thermochemical properties of ClO, BrO, IO, and their anions

A coupled cluster composite approach has been used to accurately determine the spectroscopic constants, bond dissociation energies, and heats of formation for the X1(2)II(3/2) states of the halogen oxides ClO, BrO, and IO, as well as their negative ions ClO-, BrO-, and IO-. After determining the frozen core, complete basis set (CBS) limit CCSD(T) values, corrections were added for core-valence correlation, relativistic effects (scalar and spin-orbit), the pseudopotential approximation (BrO and IO), iterative connected triple excitations (CCSDT), and iterative quadruples (CCSDTQ). The final ab initio equilibrium bond lengths and harmonic frequencies for ClO and BrO differ from their accurate experimental values by an average of just 0.0005 A and 0.8 cm-1, respectively. The bond length of IO is overestimated by 0.0047 A, presumably due to an underestimation of molecular spin-orbit coupling effects. Spectroscopic constants for the spin-orbit excited X2(2)III(1/2) states are also reported for each species. The predicted bond lengths and harmonic frequencies for the closed-shell anions are expected to be accurate to within about 0.001 A and 2 cm-1, respectively. The dissociation energies of the radicals have been determined by both direct calculation and through use of negative ion thermochemical cycles, which made use of a small amount of accurate experimental data. The resulting values of D0, 63.5, 55.8, and 54.2 kcal/mol for ClO, BrO, and IO, respectively, are the most accurate ab initio values to date, and those for ClO and BrO differ from their experimental values by just 0.1 kcal/mol. These dissociation energies lead to heats of formation, DeltaH(f) (298 K), of 24.2 +/- 0.3, 29.6 +/- 0.4, and 29.9 +/- 0.6 kcal/mol for ClO, BrO, and IO, respectively. Also, the final calculated electron affinities are all within 0.2 kcal/mol of their experimental values. Improved pseudopotential parameters for the iodine atom are also reported, together with revised correlation consistent basis sets for this atom.     

Magnetic properties of lanthanide chalcogenide semiconducting nanoparticles

To understand the importance of the band gap to the magnetic ordering in magnetic semiconductors, we have studied the effect of particle size on the ferromagnetic Curie temperature in semiconducting EuS. We have synthesized capped approximately 20 nm EuS nanoparticles using a single-source precursor, [Eu(S(2)CN(i)()Bu(2))(3)Phen] decomposed in trioctylphosphine. The nanoparticles have been characterized by X-ray powder diffraction, TEM, and magnetic susceptibility measurements as a function of temperature and field. The Curie temperature, based on Arrott plots, is depressed by 1-2 K from the bulk value.     

Robust Iterative Solution of a Class of Time-Dependent Optimal Control Problems

The fast iterative solution of optimal control problems, and in particular PDE-constrained optimization problems, has become an active area of research in applied mathematics and numerical analysis. In this paper, we consider the solution of a class of time-dependent PDE-constrained optimization problems, specifically the distributed control of the heat equation. We develop a strategy to approximate the (1, 1)-block and Schur complement of the saddle point system that results from solving this problem, and therefore derive a block diagonal preconditioner to be used within the MINRES algorithm. We present numerical results to demonstrate that this approach yields a robust solver with respect to step-size and regularization parameter. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and Crystal Structure of the Zinc Borate Zn3B4O9

The new zinc borate Zn₃B₄O₉ was synthesized at high-pressure/high-temperature conditions of 10 GPa and 1173 K in a Walker-type multianvil pressure device. It crystallizes in the space group P (no. 2) with a=5.5028(2) Å, b=6.7150(3) Å, c=7.8887(3) Å, α=83.99(1)°, β=73.38(1)°, γ=74.75(1)°, V=269.35(2) ų, and two formula units (Z=2) per unit cell. The structure was confirmed via single-crystal X-ray diffraction. Zn₃B₄O₉ can be synthesized phase pure, which is shown with a Rietveld refinement. IR-spectroscopic data of a powder sample were collected.     

ChemInform Abstract: The d0, d1 and d2 Configurations in Known and Unknown Tetrathiometal Compounds MS4n‐ (M: Mo,Tc, Ru; W,Re, Os). A Quantum Chemical Study.

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