Fast Marching Method for Calculating Reactive Trajectories for Chemical Reactions

We present a method for computing classical Newtonian trajectories that minimize the path length or transit time from reactant to product. Our approach is based on a generalization of the fast-marching method, which allows us to construct the solution of the Hamilton-Jacobi equation for the action that optimizes the desired quantity. The resulting “reactive paths” can be interpreted as reaction coordinates but, unlike more conventional choices, they contain dynamical information about the chemical system of interest.     

The solvation of iodine anions in water clusters: PES studies

We have measured the photoelectron-spectra of I^? (H₂O)_n clusters in the size range n=1–60. We have found that the first six water molecules form a solvation layer with an average 0.35 eV electrostatic stabilization of the anion. At larger cluster sizes the electrostatic stabilization of water does not fit a continuous dielectric solvent. The most stable structures of the clusters consist of internally solvated anions. In the size range n=34–40 we have found evidence for existence of cluster structures with surface solvated anions.     

Diels-Alder chemistry at furan ring functionalized solid surfaces

A substrate-independent method for Diels-Alder chemistry at solid surfaces is described for the first time.     

Adsorption of charged macromolecules at a gold electrode

Using an optical reflectometer with impinging-jet system, the adsorption from aqueous solution onto gold of three charged macromolecules has been studied: the strong linear-chain polyelectrolyte polyvinyl pyridine (PVP(+)), the fifth-generation poly(propylene imine) dendrimer DAB-64, which has a pH-dependent charge and a relatively fixed shape, and the protein lysozyme, of which both the charge and the structure-stability are dependent on solution composition. Experimental conditions that have been varied include the adsorbate concentration, electrolyte concentration, pH, and externally applied potential across the gold/solution interface. Making use of the earlier established dependency of the double layer potential of the gold substrate on solution conditions and externally applied potential, the results of measurements as a function of pH and as a function of external potential control are compared. The total set of results enables us to draw conclusions with respect to the relative importance of electrostatic interactions for the adsorption process. PVP(+) adsorption follows the electric potential of the gold/solution interface and is further determined by a rather strong nonelectrostatic affinity between segments and surface. The adsorption behavior of DAB-64 is not quite understood, but electrostatic interactions with the gold surface seem to play a minor role. For lysozyme, surface-induced conformational changes dominate the adsorption process. The extent of spreading of the molecules decreases with increasing polarity of the surface, resulting in a minimum in adsorbed amount around the point of zero potential of the gold.     

Chaos in thermal pulse combustion

An experimental thermal pulse combustor and a differential equation model of this device are shown to exhibit chaotic behavior under certain conditions. Chaos arises in the model by means of a progression of period-doubling bifurcations that occur when operating parameters such as combustor wall temperature or air/fuel flow are adjusted to push the system toward flameout. Bifurcation sequences have not yet been reproduced experimentally, but similarities are demonstrated between the dynamic features of pressure fluctuations in the model and experiment. Correlation dimension, Kolmogorov entropy, and projections of reconstructed attractors using chaotic time series analysis are demonstrated to be useful in classifying dynamical behavior of the experimental combustor and for comparison of test data to the model results. Ways to improve the model are suggested. (c) 1995 American Institute of Physics.     

Dynamics of Abelian Higgs vortices in the near Bogomolny regime

The aim of this paper is to give an analytical discussion of the dynamics of the Abelian Higgs multi-vortices whose existence was proved by Taubes ([JT82]). For a particular value of a parameter of the theory, , called the Higgs self-coupling constant, there is no force between two vortices and there exist static configurations corresponding to vortices centred at any set of points in the plane. This is known as the Bogomolny regime. We will develop some formal asymptotic expansions to describe the dynamics of these multi-vortices for close, but not equal to, this critical value. We shall then prove the validity of these asymptotic expansions. These expansions allow us to give a finite dimensional Hamiltonian system which describes the vortex dynamics. The configuration space of this system is the moduli space—the space of solutions of the static equations modulo gauge equivalence. The kinetic energy term in the Hamiltonian is obtained from the natural metric on the moduli space given by theL ² inner product of the tangent vectors. The potential energy gives the intervortex potential which is non-zero when is not given by its critical value. Thus the reduced equations for the evolution of the vortex parameters take the form of geodesics, with force terms to express the departure from the Bogomolny regime. The geodesics are geodesics on the moduli space with respect to the metric defined by theL ² inner product of the tangent vectors, in accordance with Manton's suggestion ([Man82]). This allows an understanding of the two main phenomenological issues—first of all there is the right angle scattering phenomenon, according to which two vortices passing through one another scatter through ninety degrees. Secondly there is the conjecture from numerical calculations that vortices repel for greater than the critical value, and attract for less than this value. The results of this paper allow a rigorous understanding of the right angle scattering phenomenon ([Sam92, Hit88]) and reduce the question of attraction or repulsion in the near Bogomolny regime to an understanding of the potential energy term in the Hamiltonian ([JR79]).