Band gaps and structural properties of graphene halides and their derivates: a hybrid functional study with localized orbital basis sets

Density functional theory calculations of the electronic structure of graphane and stoichiometrically halogenated graphene derivatives (fluorographene and other analogous graphene halides) show: (i) localized orbital basis sets can be successfully and effectively used for such two-dimensional materials; (ii) several functionals predict that the band gap of graphane is greater than that of fluorographene, whereas HSE06 gives the opposite trend; (iii) HSE06 functional predicts quite good values of band gaps with respect to benchmark theoretical and experimental data; (iv) the zero band gap of graphene is opened by hydrogenation and halogenation and strongly depends on the chemical composition of mixed graphene halides; (v) the stability of graphene halides decreases sharply with increasing size of the halogen atom--fluorographene is stable, whereas graphene iodide spontaneously decomposes. In terms of band gap and stability, the C(2)FBr and C(2)HBr derivatives seem to be promising materials, e.g., for (opto)electronics applications, because their band gaps are similar to those of conventional semiconductors, and they are expected to be stable under ambient conditions. The results indicate that other fluorinated compounds (C(a)H(b)F(c) and C(a)F(b)Y(c), Y = Cl, Br, I) are stable insulators.     

On the convergence of a dual-primal substructuring method

Summary.   In the Dual-Primal FETI method, introduced by Farhat et al. [5], the domain is decomposed into non-overlapping subdomains, but the degrees of freedom on crosspoints remain common to all subdomains adjacent to the crosspoint. The continuity of the remaining degrees of freedom on subdomain interfaces is enforced by Lagrange multipliers and all degrees of freedom are eliminated. The resulting dual problem is solved by preconditioned conjugate gradients. We give an algebraic bound on the condition number, assuming only a single inequality in discrete norms, and use the algebraic bound to show that the condition number is bounded by for both second and fourth order elliptic selfadjoint problems discretized by conforming finite elements, as well as for a wide class of finite elements for the Reissner-Mindlin plate model. Received January 20, 2000 / Revised version received April 25, 2000 / Published online December 19, 2000     

Chemical vapour deposition of germanium-containing films by IR laser-induced decomposition of ethoxy(trimethyl)germane

Carbon Dioxide (CO₂) laser-induced decomposition of ethoxy(trimethyl)germane (ETG) results in a substantial stripping of organic substituents from germanium and leads to deposition of organogermanium films, the composition of which is dependent on the mode of laser irradiation. Direct absorption of laser radiation in ETG affords material rich in Germanium, while a sulfur hexafluoride (SF₆)-photosensitized process produces a deposit composed of Germanium, Carbon, Hydrogen and Oxygen. The deposited materials can be modified by chemical reactions with acetic anhydride and atmospheric moisture.     

The first synthesis and cytostatic activity of novel 6-(fluoromethyl)purine bases and nucleosides

Two alternative approaches to the synthesis of novel 6-(fluoromethyl)purine bases and nucleosides are described either by direct deoxyfluorination or by multistep functional group transformations starting from 6-(hydroxymethyl)purines. 6-(fluoromethyl)purine ribonucleoside displayed significant cytostatic effects.     

Catalytic photooxidation of 4-methoxybenzyl alcohol with a flavin-zinc(II)-cyclen complex

Flavin-zinc(II)-cyclen 10 contains a covalently linked substrate binding site (zinc(II)-cyclen) and a chromophore unit (flavin). Upon irradiation, compound 10 effectively oxidizes 4-methoxybenzyl alcohol (11-OCH3) to the corresponding benzaldehyde both in water and in acetonitrile. In the presence of air, the reduced flavin 10-H2 is reoxidized, and so catalytic amounts of 10 are sufficient for alcohol conversion. The mechanism of oxidation is based on photoinduced electron transfer from the coordinated benzyl alcohol to the flavin chromophore. This intramolecular process provides a much higher photooxidation efficiency, with quantum yields 30 times those of the comparable intermolecular process with a flavin chromophore without a binding site. For the reaction in buffered aqueous solution a quantum yield of Phi = 0.4 is observed. The turnover number in acetonitrile is increased (up to 20) by high benzyl alcohol concentrations. The results show that the covalent combination of a chromophore and a suitable binding site may lead to photomediators more efficient than classical sensitizer molecules.