Transfer measurements for the Ti+Ni systems at near barrier energies

Large enhancements have been observed in the sub-barrier fusion cross sections for Ti+Ni systems in our previous studies. Coupled channel calculations incorporating couplings to 2⁺ and 3⁻ states failed to explain these enhancements completely. A possibilty of transfer channels contributing to the residual enhancements had been suggested. In order to investigate the role of relevant transfer channels, measurements of one- and two-nucleon transfer were carried out for ^46,48Ti+⁶¹Ni systems. The present paper gives the results of these studies.     

l‐Valyl‐l‐serine trihydrate

The valine side chains in the crystal structure of the title compound [systematic name: 2‐(2‐ammonio‐3‐methyl­butan­amido)‐3‐hydroxy­propano­ate tri­hydrate], C₈H₁₆N₂O₄·3H₂O, stack along an a axis of 4.77 Å to form hydro­phobic columns surrounded by remarkable water/hydroxyl shells. The peptide main chains are connected by hydrogen bonds in two‐dimensional layers. The peptide mol­ecules in each layer are related only by translation, and generate a very rare pattern. This is rendered possible through the formation of the shortest C^α—H·O(carboxyl­ate) inter­action ever recorded.     

π-Electron currents in fixed π-sextet aromatic benzenoids

In view of different patterns of π-electron density currents in benzenoid aromatic compounds it is of interest to investigate the pattern of ring currents in various classes of compounds. Recently such a study using a graph theoretical approach to calculating CC bond currents was reported for fully benzenoid hydrocarbons, that is, benzenoid hydrocarbons which have either π-sextets rings or “empty” rings in the terminology of Clar. In this contribution we consider π-electron currents in benzenoid hydrocarbons which have π-electron sextets and C=C bonds fully fixed. Our approach assumes that currents arise from contributions of individual conjugated circuits within the set of Kekulé valence structures of these molecules.     

π‐Electron currents in larger fully aromatic benzenoids

Recently, we have reported on calculation of π‐electron ring currents in several smaller fully benzenoid hydrocarbons having up to eight fused benzene rings and five Clar π‐aromatic sextets. In contrast to early HMO ring current calculations and more recent ab initio calculations of π‐electron density, our current calculations are based on a graph theoretical model in which contributions to ring currents comes from currents associated with individual conjugated circuits. In this contribution, we consider several larger fully benzenoid hydrocarbons having from 9 to 13 fused rings and from six or seven π‐aromatic sextets. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Three-Phase Flow Modelling Using Pore-Scale Capillary Pressures and Relative Permeabilities for Mixed-Wet Media at the Continuum-Scale

When regions of three-phase flow arise in an oil reservoir, each of the flow parameters, i.e. capillary pressures and relative permeabilities, are generally functions of two phase saturations and depend on the wettability state. The idea of this work is to generate consistent pore-scale based three-phase capillary pressures and relative permeabilities. These are then used as input to a 1-D continuum core- or reservoir-scale simulator. The pore-scale model comprises a bundle of cylindrical capillary tubes, which has a distribution of radii and a prescribed wettability state. Contrary to a full pore-network model, the bundle model allows us to obtain the flow functions for the saturations produced at the continuum-scale iteratively. Hence, the complex dependencies of relative permeability and capillary pressure on saturation are directly taken care of. Simulations of gas injection are performed for different initial water and oil saturations, with and without capillary pressures, to demonstrate how the wettability state, incorporated in the pore-scale based flow functions, affects the continuum-scale displacement patterns and saturation profiles. In general, wettability has a major impact on the displacements, even when capillary pressure is suppressed. Moreover, displacement paths produced at the pore-scale and at the continuum-scale models are similar, but they never completely coincide.     

Moderately branched ultra‐high molecular weight polyethylene by using N,N′‐nickel catalysts adorned with sterically hindered dibenzocycloheptyl groups

Five examples of unsymmetrical 1,2‐bis (arylimino) acenaphthene ( L1 – L5 ), each containing one N‐2,4‐bis (dibenzocycloheptyl)‐6‐methylphenyl group and one sterically and electronically variable N‐aryl group, have been used to prepare the N,N′‐nickel (II) halide complexes, [1‐[2,4‐{(C₁₅H₁₃}₂–6‐MeC₆H₂N]‐2‐(ArN)C₂C₁₀H₆]NiX₂ (X = Br: Ar = 2,6‐Me₂C₆H₃ Ni1 , 2,6‐Et₂C₆H₃ Ni2 , 2,6‐i‐Pr₂C₆H₃ Ni3 , 2,4,6‐Me₃C₆H₂ Ni4 , 2,6‐Et₂–4‐MeC₆H₂ Ni5 ) and (X = Cl: Ar = 2,6‐Me₂C₆H₃ Ni6 , 2,6‐Et₂C₆H₃ Ni7 , 2,6‐i‐Pr₂C₆H₃ Ni8 , 2,4,6‐Me₃C₆H₂ Ni9 , 2,6‐Et₂–4‐MeC₆H₂ Ni10 ), in high yield. The molecular structures Ni3 and Ni7 highlight the extensive steric protection imparted by the ortho‐dibenzocycloheptyl group and the distorted tetrahedral geometry conferred to the nickel center. On activation with either Et₂AlCl or MAO, Ni1 – Ni10 exhibited very high activities for ethylene polymerization with the least bulky Ni1 the most active (up to 1.06  ×  10⁷ g PE mol^?1(Ni) h^?1 with MAO). Notably, these sterically bulky catalysts have a propensity towards generating very high molecular weight polyethylene with moderate levels of branching and narrow dispersities with the most hindered Ni3 and Ni8 affording ultra‐high molecular weight material (up to 1.5  ×  10⁶ g mol^?1). Indeed, both the activity and molecular weights of the resulting polyethylene are among the highest to be reported for this class of unsymmetrical 1,2‐bis (imino)acenaphthene‐nickel catalyst.     

Symmetry properties of chemical graphs VIII. On complementarity of isomerization modes

Isomerization mode defines the process of interconversion of one isomer into another. Several mechanisms are conceivable for degenerate rearrangements and, in general, lead to a distinctive network of relations between participating isomers. Here we consider selected modes which are complementary in the sense that if mode 1 transforms an isomer A into B, C, D etc., then mode 2 transforms the same isomer A into X, Y, Z, etc., which includes all isomers not comprised by the first mode. Physico-chemical complementarity can be translated into mathematical complementarity of associated chemical graphs. This allows us to use the tool of Graph Theory. One example of graph theoretical use is the theorem that graph G and its complement G have the same automorphism group (i.e., the same symmetry). We have shown that a close examination of a graph and its complement and their components allows us to recognize the automorphism group in some complex cases without resorting to canonical numbering or other involved procedures, and even allows us to determine isomorphism of different processes.Dedicated to Professor Kurt Mislow of Princeton UniversityOperated for the U.S. Department of Energy by Iowa State University under contract W-7405-Eng-82. Supported in part by the Office of the Director.     

Molecular bonding profiles

We present a refinement of recently proposed characterization of molecules based on a sequence of powers of interatomic separations referred to as molecular profiles. The molecular profiles and closely related shape profiles were based on the averaging contributions arising from different powers of interatomic distances for atoms in a molecule or atoms at the molecular periphery, respectively. Consequently, molecular models in which atoms have the same set of coordinates but different bonding patterns will result in identical molecular profiles. In this article we outline a refinement of molecular profiles in which the bonding pattern in a molecule is fully acknowledged. This is accomplished by adding ghost sites along chemical bonds. The distance-based invariants of the augmented matrix reflect the bonding pattern of a structure giving different molecular profiles for molecules having the same atomic coordinates but different bondings. The procedure is general and applies to two-dimensional and three-dimensional molecular skeletons. Equally, the approach can be applied to van der Waals-type molecular surfaces and molecular contours of equal electron densities in order to obtain characterization of more realistic molecular models.Dedicated to a leading graph theorist, Professor R. C. Read, for sharing his mathematical talents on chemical structures.