Optimized intermolecular potential for aromatic hydrocarbons based on anisotropic united atoms. III. Polyaromatic and naphthenoaromatic hydrocarbons

In this third article of the series, a new anisotropic united atoms (AUA) intermolecular potential parameter set has been proposed for the carbon force centers connecting the aromatic rings of polyaromatic hydrocarbons to predict thermodynamic properties using both the Gibbs ensemble and NPT Monte Carlo simulations. The model uses the same parameters as previous AUA models used for the aromatic CH force centers. The optimization procedure is based on the minimization of a dimensionless error criterion incorporating various thermodynamic data of naphthalene at 400 and 550 K. The new model has been evaluated on a series of polyaromatic and naphthenoaromatic hydrocarbons over a wide range of temperatures up to near-critical conditions. Vaporization enthalpy, liquid density, and normal boiling temperature are reproduced with good accuracy. The new potential parameters have also been tested successfully on toluene, 1,3,5-trimethylbenzene, styrene, m-xylene, n-hexylbenzene, and n-dodecylbenzene to demonstrate their transferability to alkylbenzenes.     

Structural investigation of high-valent manganese-salen complexes by UV/Vis,Raman, XANES,and EXAFS spectroscopy

XANES and EXAFS spectroscopic studies at the Mn-K- and Br-K-edge of reaction products of (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride ([(salen)Mn(III)Cl], 1) and (S,S)-(+)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) bromide ([(salen)Mn(III)Br], 2) with 4-phenylpyridine N-oxide (4-PPNO) and 3-chloroperoxybenzoic acid (MCPBA) are reported. The reaction of the Mn(III) complexes with two equivalents of 4-PPNO leads to a hexacoordinated compound, in which the manganese atom is octahedrally coordinated by four oxygen/nitrogen atoms of the salen ligand at an average distance of approximately 1.90 A and two additional, axially bonded oxygen atoms of the 4-PPNO at 2.25 A. The oxidation state of this complex was determined as approximately +IV by a comparative study of Mn(III) and Mn(V) reference compounds. The green intermediate obtained in reactions of MCPBA and solutions of 1 or 2 in acetonitrile was investigated with XANES, EXAFS, UV/Vis, and Raman spectroscopy, and an increase of the coordination number of the manganese atoms from 4 to 5 and the complete abstraction of the halide was observed. A formal oxidation state of IV was deduced from the relative position of the pre-edge 1s-->3d feature of the X-ray absorption spectrum of the complex. The broad UV/Vis band of this complex in acetonitrile with lambda(max)=648 nm was consistent with a radical cation structure, in which a MCPBA molecule was bound to the Mn(IV) central atom. An oxomanganese(V) or a dimeric manganese(IV) species was not detected.     

Aggregate, Polymer and Cluster Formation from Metal-Imino Carboxylate Complexes

Reaction of tris-(2-aminoethyl)amine (tren) andthe sodium salt of an -ketocarboxylic acid, typically sodium pyruvate, affordsin the presence of a lanthanide ion aseries of complexes and aggregates includingmononuclear, cyclic tetranuclear and polymerspecies of [L¹]^3- ([L¹]^3-=N[CH₂CH₂N=C(CH₃)COO^-]³).The aggregation of these and related d-block elementcomplexes with Na⁺ ions leadsto the formation of polymeric materials, and thefactors influencing the formation and controlof these various aggregation states are discussed.Metal cations also template the aggregationof the fragment [Ni(L²)] ([L²]^2- =CH₂[CH₂N = C(CH₃)COO^-]₂)to give, in high yield, the polynuclearaggregates {[Ni(L²)]₆M}^x+(M = Nd, Pr, Ce, La, x = 3; M = Sr, Ba, x = 2). The structures of{[Ni(L²)]₆M}^x+ show aninterstitial twelve co-ordinate, icosahedralcation M^x+ encapsulated by six [Ni(L²)]fragments. In the presence ofNa⁺, aggregation of [Ni(L²)] fragments affords {[Ni(L²)]₉Na₄(H₂O)(MeOH)(ClO₄)}³⁺ thestructure of whichshows four Na⁺ ions templating the formation ofa distorted tricapped trigonal prismatic[Ni(L²)]₉ cage. Thus, control overconstruction of various polynuclear cages viaself-assembly at octahedral junctions can beachieved using main group, transition metaland lanthanide ion templates.     

Direct solid sample analysis of geological samples with SS-GF-AAS and use of 3D calibration

These results from direct solid-sample trace-element analysis, with 3D calibration, follow those of earlier publications. Cd, Cr, Cu, Ni, Pb, and Zn have been determined in complex inorganic powder samples, e.g. sediments, soils, rocks, and minerals. The measurements were performed with two SS-GF-AAS spectrometers which differ in the type of graphite furnace (transverse and longitudinal tube) and the background-correction technique (with and without the Zeeman system). The performance of the 3D calibration method was optimized by systematic investigation and the 2D- and 3D calibration techniques were compared. Another feature is the determination of confidence limits of the 3D calibration. This calibration error was calculated by the statistical bootstrap method. The results of calibration experiments and the precision and accuracy of the determination of trace elements in CRMs show that 3D calibration becomes increasingly essential as the refractory character of the analyte increases. Although there are large differences between the state of development and technical performance of the instruments used, 3D-calibration works with both SS-GF-AAS spectrometers.     

Coloring linear hypergraphs: the Erdős–Faber–Lovász conjecture and the Combinatorial Nullstellensatz

Designs, Codes and Cryptography - The long-standing Erdős–Faber–Lovász conjecture states that every n-uniform linear hypergaph with n edges has a proper vertex-coloring using...     

On permutations of central quadrics which preserve an inner distance

Letq be a regular quadratic form on a vector space (V, $\mathbb{F}$ ) and assume dimV ≥ 4 and ¦ $\mathbb{F}$ ¦ ≥ 4. We consider a permutation ? of the central affine quadric $\mathcal{F}$ := {x εV ¦q(x) = 1} such that $$(*)x \cdot y = \mu \Leftrightarrow x^\varphi \cdot y^\varphi = \mu \forall x,y\varepsilon \mathcal{F}$$ holds true, where μ is a fixed element of $\mathbb{F}$ and where “·” is the scalar product associated withq. We prove that ? is induced (in a certain sense) by a semi-linear bijection (σ,?): (V, $\mathbb{F}$ ) → (V, $\mathbb{F}$ ) such thatq o ?o q, provided $\mathcal{F}$ contains lines and the pair (μ, $\mathbb{F}$ ) has additional properties if there ar no planes in $\mathcal{F}$ . The cases μ,≠ 0 and μ = 0 require different techniques.     

Orientations of chain groups

We prove generalizations to chain groups, of Minty's Arc Colouring Lemma and its extension, the well-known Farkas Lemma. In these the orientation of the edges is replaced by an arbitrary chain.A function on a chain groupN isrepresentable if there exists a chainR such that (X)=R·X for allXN. Anorientation is a chain with values ±1. We prove that for a regular chain group a linear function that is representable by an orientation for each chainXN locally, is representable by an orientation globally.     

Investigation of the40Ca(γ,N) reaction at 60 MeV

The values of the angle-integrated cross section for the decay to various low-lying states in³⁹K following the⁴⁰Ca(,) reaction at a mean photon energy of 60 MeV are reported on, together with the values of the reduced Legendre coefficientsa _i . The⁴⁰Ca(,gp) and⁴⁰Ca(,n) reactions yield the same angular cross-section values and these agree with the corresponding RPA-calculations.Senior Research Associate NFWO