Activation/Inhibition Effects during the Coelectrodeposition of PtAg Nanoparticles: Application for ORR in Alkaline Media

PtAg bimetallic nanoparticles for oxygen reduction reaction (ORR) in alkaline media were prepared by pulse electrodeposition (PED). During PED the reduction of Ag⁺ ions predominates, thus an increased Ag content in the co‐deposit is accomplished. The mechanism for this anomalous co‐deposition was elucidated by potential pulse experiments, which revealed that nuclei formation mainly occurs via the reduction of Pt²⁺ ions. The growth of the particles is diffusion controlled leading to the formation of a Ag shell covering a PtAg alloyed region. However, the shell is not growing homogeneously on the PtAg alloy. Hence, regions of the PtAg alloy are exposed, which exhibit an enhanced ORR activity compared to a pure Ag surface.     

The micromechanics of three‐dimensional collagen‐I gels

We study the micromechanics of collagen‐I gel with the goal of bridging the gap between theory and experiment in the study of biopolymer networks. Three‐dimensional images of fluorescently labeled collagen are obtained by confocal microscopy, and the network geometry is extracted using a 3D network skeletonization algorithm. Each fiber is modeled as an elastic beam that resists stretching and bending, and each crosslink is modeled as torsional spring. The stress–strain curves of networks at three different densities are compared with rheology measurements. The model shows good agreement with experiment, confirming that strain stiffening of collagen can be explained entirely by geometric realignment of the network, as opposed to entropic stiffening of individual fibers. The model also suggests that at small strains, crosslink deformation is the main contributer to network stiffness, whereas at large strains, fiber stretching dominates. As this modeling effort uses networks with realistic geometries, this analysis can ultimately serve as a tool for understanding how the mechanics of fibers and crosslinks at the microscopic level produce the macroscopic properties of the network. © 2010 Wiley Periodicals, Inc. Complexity 16: 22‐28, 2011     

Fortran codes for the correlation functions of hard sphere fluids

Our Fortran codes for hard sphere fluids and their mixtures for the correlation functions that arise from the Percus–Yevick theory and the Verlet–Weis semi-empirical correction have proven useful during a period of nearly four decades and continue to be useful. In order to make these codes even more widely available, a brief summary is presented here and listings of these codes are given in the electronically accessible Supplementary Material to this paper.     

The Yang-Mills Heat Semigroup on Three-Manifolds with Boundary

Long time existence and uniqueness of solutions to the Yang-Mills heat equation is proven over a compact 3-manifold with smooth boundary. The initial data is taken to be a Lie algebra valued connection form in the Sobolev space H ₁. Three kinds of boundary conditions are explored, Dirichlet type, Neumann type and Marini boundary conditions. The last is a nonlinear boundary condition, specified by setting the normal component of the curvature to zero on the boundary. The Yang-Mills heat equation is a weakly parabolic nonlinear equation. We use gauge symmetry breaking to convert it to a parabolic equation and then gauge transform the solution of the parabolic equation back to a solution of the original equation. Apriori estimates are developed by first establishing a gauge invariant version of the Gaffney-Friedrichs inequality. A gauge invariant regularization procedure for solutions is also established. Uniqueness holds upon imposition of boundary conditions on only two of the three components of the connection form because of weak parabolicity. This work is motivated by possible applications to quantum field theory.     

The Formation of Pd Nanocrystals from Pd2(dba)3 Microcrystals

As‐grown platelets formed from tris‐(dibenzylideneacetone) dipalladium(0) [Pd₂(dba)₃] precursor in the presence of Pd17 RNA are investigated before and after thermal annealing. Results show that as‐grown platelets are disordered crystals of Pd₂(dba)₃ containing 1?2 nm Pd clusters and platelets grown in the absence of RNA are morphologically and structurally similar to those formed with RNA. The initially formed crystals are so sensitive to environmental variables that the degree of crystallinity can not be determined accurately by electron diffraction. X‐ray crystallography on as‐grown platelets gives a crystal structure consistent with Pd₂(dba)₃, but reveals a composition of ≈Pd_1.07(dba)₃, indicating one Pd atom in Pd₂(dba)₃ is lost from the structure. Both electron beam and thermally induced decomposition of as‐grown Pd₂(dba)₃ platelets having a hexagonal habit on the micrometer scale produces elemental Pd platelets having a hexagonal habit on the nanometer scale. These hexagonal platelets are composed of a partially sparse form of Pd₂(dba)₃ that is initially crystalline but rapidly degrades due to the loss of Pd atoms from organic ligand cages. Once released, Pd atoms aggregate to form Pd clusters, which grow and transform into well‐formed Pd nanocrystals under electron‐beam irradiation or through thermal annealing.     

On r*-sequenceability and symmetric harmoniousness of groups. II

In this paper we investigate symmetric harmoniousness of groups and connections of this concept to the R*-sequenceability of groups. We prove that, under suitable assumptions, the direct product of a symmetric harmonious group with a group that is R*-sequenceable is R*-sequenceable; we discuss the symmetric harmoniousness of abelian and of nilpotent groups; we also prove that, for a fixed odd prime p, all but possibly finitely many of the nonabelian groups of order pq (q prime, q ≡ 1 (mod p)) are symmetric harmonious. © 1995 John Wiley & Sons, Inc.     

A General Deterministic Treatment of Derivatives in Particle Methods

A unified approach to approximating spatial derivatives in particle methods using integral operators is presented. The approach is an extension of particle strength exchange, originally developed for treating the Laplacian in advection–diffusion problems. Kernels of high order of accuracy are constructed that can be used to approximate derivatives of any degree. A new treatment for computing derivatives near the edge of particle coverage is introduced, using “one-sided” integrals that only look for information where it is available. The use of these integral approximations in wave propagation applications is considered and their error is analyzed in this context using Fourier methods. Finally, simple tests are performed to demonstrate the characteristics of the treatment, including an assessment of the effects of particle dispersion, and their results are discussed.     

Krylov type subspace methods for matrix polynomials

We consider solving eigenvalue problems or model reduction problems for a quadratic matrix polynomial Iλ² − Aλ − B with large and sparse A and B. We propose new Arnoldi and Lanczos type processes which operate on the same space as A and B live and construct projections of A and B to produce a quadratic matrix polynomial with the coefficient matrices of much smaller size, which is used to approximate the original problem. We shall apply the new processes to solve eigenvalue problems and model reductions of a second order linear input-output system and discuss convergence properties. Our new processes are also extendable to cover a general matrix polynomial of any degree.