The role of intermolecular polarization for the stability of lithium intercalation compounds of alpha- and beta-perylene

Lithium intercalation compounds of alpha- and beta-perylene are investigated by photoelectron spectroscopy. Spectroscopic data together with a Born-Haber cycle provide information on the formation enthalpy of those materials. This approach allows understanding the amount of charge transferred from the alkali metal atoms to the pi system, and illuminates the role of molecular versus solid-state properties in the formation of the intercalation compounds. In the bulk of alpha-perylene material, molecular dimerization survives upon intercalation which reduces the Madelung energy of the intercalation compound but increases the electron-accepting capability of the organic system and facilitates the ionization of lithium atoms in the molecular solid environment. The lower ionization potential results in a larger charge transfer (about two electrons per molecule) in alpha-perylene compared to the monomeric system, beta-perylene.     

Cationic Bismuth Aminotroponiminates: Charge Controls Redox Properties

The behavior of the redox-active aminotroponiminate (ATI) ligand in the coordination sphere of bismuth has been investigated in neutral and cationic compounds, [Bi(ATI)₃] and [Bi(ATI)₂L_n][A] (L=neutral ligand; n=0, 1; A=counteranion). Their coordination chemistry in solution and in the solid state has been analyzed through (variable-temperature) NMR spectroscopy, line-shape analysis, and single-crystal X-ray diffraction analyses, and their Lewis acidity has been evaluated by using the Gutmann–Beckett method (and modifications thereof). Cyclic voltammetry, in combination with DFT calculations, indicates that switching between ligand- and metal-centered redox events is possible by altering the charge of the compounds from 0 in neutral species to +1 in cationic compounds. This adds important facets to the rich redox chemistry of ATIs and to the redox chemistry of bismuth compounds, which is, so far, largely unexplored.     

Investigation of novel and reinvestigation of known cyclopentadienylphosphanes: News on [1,5] sigmatropic rearrangements

Ph₂P(C₅HMe₄) (1) was found to undergo a prototropic rearrangement contrary to previous reports. The first detailed investigation of a cyclopentadienylphosphane to undergo such a reaction is presented. One of the two tautomers of 1 which were observed represents the kinetic product, the other one is the thermodynamic product. The two isomers exhibit pronounced differences with respect to their chemical reactivity. Thermodynamic and kinetic data of the isomerisation process were determined. A novel, electron rich cyclopentadienylphosphane, the phosphorus diamide (Me₂N)₂P(C₅HMe₄) (2), was synthesised and was also found to undergo a prototropic rearrangement. The characteristics of the isomerisation process are fully consistent with the findings on 1. The molecular structure of the kinetic product of 2 was established by means of single crystal X-ray diffraction analysis. Me₂P(C₅H₄tBu) (3) is presented as another novel cyclopentadienylphosphane. The mixture of isomers of 3 in thermodynamic equilibrium was investigated in detail with respect to the molecular structures of the tautomers. The results of this study suggested a reinvestigation of the parent compound Ph₂P(C₅H₄tBu) (4) and findings differing from an earlier report in some details are presented.     

Quantum annealing of the graph coloring problem

Quantum annealing extends simulated annealing by introducing artificial quantum fluctuations. The path-integral Monte Carlo version chosen is population-based and designed to be implemented on a classical computer. Its first application to the graph coloring problem is presented in this paper. It is shown by experiments that quantum annealing can outperform classical thermal simulated annealing for this particular problem. Moreover, quantum annealing proved competitive when compared with the best algorithms on most of the difficult instances from the DIMACS benchmarks. The quantum annealing algorithm has even found that the well-known benchmark graph dsjc1000.9 has a chromatic number of at most 222. This is an improvement on its best upper-bound from a large body of literature.     

Synthesis and characterization of hollow ��-Fe2O3 sub-micron spheres prepared by sol�Cgel

In this work we report the preparation of magnetic hematite hollow sub-micron spheres (??-Fe₂O₃) by colloidal suspensions of ferric nitrate nine-hydrate (Fe(NO₃)₃·9H₂O) particles in citric acid solution by following the sol?Cgel method. After the gel formation, the samples were annealed at different temperatures in an oxidizing atmosphere. Annealing at 180°C resulted in an amorphous phase, without iron oxide formation. Annealing at 250°C resulted in coexisting phases of hematite, maghemite and magnetite, whereas at 400°C, only hematite and maghemite were found. Pure hematite hollow sub-micron spheres with porous shells were formed after annealing at 600°C. The characterization was performed by X-ray diffraction (XRD), Mössbauer spectroscopy (MS) and scanning electron microscopy (SEM).     

Electron image series reconstruction of twin interfaces in InP superlattice nanowires

The twin interface structure in twinning superlattice InP nanowires with zincblende structure has been investigated using electron exit wavefunction restoration from focal series images recorded on an aberration-corrected transmission electron microscope. By comparing the exit wavefunction phase with simulations from model structures, it was possible to determine the twin structure to be the ortho type with preserved In-P bonding order across the interface. The bending of the thin nanowires away from the intended 110 axis could be estimated locally from the calculated diffraction pattern, and this parameter was successfully taken into account in the simulations.