Vibrational EELS and DFT study of propionic acid and pyruvic acid on Ni(1 0 0): Effects of keto group substitution on room-temperature adsorption and thermal chemistry

The room-temperature adsorption and thermally induced processes of propionic acid and pyruvic acid on Ni(1 0 0) have been investigated by electron energy loss spectroscopy (EELS). Computational vibrational analysis of the optimized bidentate structures for acid-Ni model complexes (involving the organic acid and a Ni atom) has been performed by using the two-layer ONIOM method with the Density Functional Theory and used to interpret the vibrational EELS data. Dehydrogenation of the hydroxyl group is found to result in bonding of the carboxylate group in the propionate and pyruvate adspecies to either a single Ni surface atom in a bidentate configuration or two neighbouring Ni atoms in a bridge configuration. Given the similarities in the total energies and related vibrational frequencies obtained by the calculations in the case of pyruvate adspecies, it is difficult to differentiate the alternate adsorption structure, in which the keto O and hydroxyl O atoms are bonded to a Ni atom in a five-member chelate ring configuration. Furthermore, temperature-dependent EELS studies show that both the propionate and pyruvate adspecies could decompose upon annealing to above 400 K and further dissociate to CO adspecies above 550 K and to C and/or O above 600 K.     

Algorithms for finding connected separators between antipodal points

A set (or a collection of sets) contained in the Euclidean space Rm is symmetric if it is invariant under the antipodal map. Given a symmetric unicoherent polyhedron X (like an n-dimensional cube or a sphere) and an odd real function f defined on vertices of a certain symmetric triangulation of X, we algorithmically construct a connected symmetric separator of X by choosing a subcollection of the triangulation. Each element of the subcollection contains the vertices v and u such that f(v)f(u)?0.     

On the moduli spaces of multipolygonal linkages in the plane

One can form a polygonal linkage by identifying initial and terminal points of two free linkages. Likewise, one can form a multipolygonal linkage by identifying initial and terminal points of three free linkages. The geometric and topological properties of moduli spaces of multipolygonal linkages in the plane are studied. These spaces are compact algebraic varieties. Some conditions under which these spaces are smooth manifolds, cross products or disjoint unions of moduli spaces of polygonal linkages, or connected, are determined. Dimensions in smooth manifold cases and some Euler characteristics are computed. A classification of generic multiquadrilateral linkages is also made.     

Separable subgroups of mapping class groups

We investigate separability questions for the mapping class group of a surface. While this group is not subgroup separable in general, we prove a large family of interesting subgroups are separable. This includes many classically studied subgroups such as solvable subgroups, Heegaard and Handlebody groups, geometric subgroups, and all the terms in the Johnson filtration.     

Nonminimal sets,their projections and integral representations of stable processes

New criteria are provided for determining whether an integral representation of a stable process is minimal. These criteria are based on various nonminimal sets and their projections, and have several advantages over and shed light on already available criteria. In particular, they naturally lead from a nonminimal representation to the one which is minimal. Several known examples are considered to illustrate the main results. The general approach is also adapted to show that the so-called mixed moving averages have a minimal integral representation of the mixed moving average type.     

Paradigms and Paradoxes: Energetics of Aqueous Oxyanions of Nonmetals and Metalloids

The enthalpies of formation of simple nonmetal or metalloid oxyanions in aqueous solution are discussed. Archival values are cited and estimates are made. Trends prove evasive.     

Sobolev-Type Classes of Functions with Values in a Metric Space. II

We prove equivalence of the definitions by the author and by Korevaar and Schoen of the Sobolev classes of mappings of a domain of an arithmetic n-dimensional space to a metric space.     

Multiple harmonic series related to multiple Euler numbers

In this paper, we define the multiple Euler numbers and consider some multiple harmonic series of Mordell-Tornheim's type, which is a partial sum of the Mordell-Tornheim zeta series defined by Matsumoto. Indeed, we prove a certain reducibility of these series as well as the multiple zeta values.     

CuPc molecules adsorbed on Au(1 1 0)-(1 × 2): growth morphology and evolution of valence band states

We present the growth morphology, the long-range ordering, and the evolution of the valence band electronic states of ultrathin films of copper phthalocyanine (CuPc) deposited on the Au(1 1 0)-(1 × 2) reconstructed surface, as a function of the organic molecule coverage. The low energy electron diffraction patterns present a (5 × 3) reconstruction from the early adsorption stages. High-resolution UV photoelectron spectroscopy data show the disappearance of the Au surface states related to the (1 × 2) reconstruction, and the presence of new electronic features related to the molecule-substrate interaction and to the CuPc molecular states. The CuPc highest occupied molecular orbital gradually emerges in the valence band, while the interface electronic states are quenched, upon increasing the coverage.     

The convex hull property and topology of hypersurfaces with nonnegative curvature

We prove that, in Euclidean space, any nonnegatively curved, compact, smoothly immersed hypersurface lies outside the convex hull of its boundary, provided the boundary satisfies certain required conditions. This gives a convex hull property, dual to the classical one for surfaces with nonpositive curvature. A version of this result in the nonsmooth category is obtained as well. We show that our boundary conditions determine the topology of the surface up to at most two choices. The proof is based on uniform estimates for radii of convexity of these surfaces under a clipping procedure, a noncollapsing convergence theorem, and a gluing procedure.