Optical spectra and laser-induced dissociation of supported Na particles

This paper reports new results on the optical spectra of Na particles and on laser-induced photodissociation of Na atoms from the surface of these particles. In continuation of our earlier studies we have performed experiments to elucidate the mechanism of thenonthermal dissociation process. Furthermore, theoretical calculations have been carried out with the goal to correlate the wavelength dependence of the photodissociation yield with the optical absorption spectra of the metal particles. In addition, manipulation of the size distribution of metal particles on supports is outlined as an application of the effect. This allows for the preparation of very special surfaces with novel physical and chemical properties.     

Ordered nanostructured ceramic–metal composites through multifunctional block copolymer-metal nanoparticle self-assembly

A novel strategy for fabrication of ordered ceramic–metal nanocomposites was demonstrated by multifunctional block copolymer/metal nanoparticle self-assembly. Hybrid organic–inorganic block copolymer poly(3-methacryloxypropyl-T8-heptaisobutyl-polyhedral oligomeric silsesquioxane-block-N,N-dimethylaminoethyl methacrylate) was synthesized and used as a bi-functional structure directing agent for ligand-stabilized platinum nanoparticles to form ordered organic–inorganic nanocomposites with dense loading of inorganic species in both microphase separated domains. Subsequently, thin films of the hybrid material were converted to ordered silica (ceramic)–platinum (metal) nanocomposites via UV-assisted ozonolysis. This is the first time ordered ceramic–metal nanocomposites were achieved through a bottom-up approach, opening up opportunities for the design and synthesis of a broad range of ordered inorganic–inorganic nanocomposites.     

A smoothing-regularization approach to mathematical programs with vanishing constraints

We consider a numerical approach for the solution of a difficult class of optimization problems called mathematical programs with vanishing constraints. The basic idea is to reformulate the characteristic constraints of the program via a nonsmooth function and to eventually smooth it and regularize the feasible set with the aid of a certain smoothing- and regularization parameter t>0 such that the resulting problem is more tractable and coincides with the original program for t=0. We investigate the convergence behavior of a sequence of stationary points of the smooth and regularized problems by letting t tend to zero. Numerical results illustrating the performance of the approach are given. In particular, a large-scale example from topology optimization of mechanical structures with local stress constraints is investigated.     

Stationary conditions for mathematical programs with vanishing constraints using weak constraint qualifications

We consider a class of optimization problems that is called a mathematical program with vanishing constraints (MPVC for short). This class has some similarities to mathematical programs with equilibrium constraints (MPECs for short), and typically violates standard constraint qualifications, hence the well-known Karush-Kuhn-Tucker conditions do not provide necessary optimality criteria. In order to obtain reasonable first order conditions under very weak assumptions, we introduce several MPVC-tailored constraint qualifications, discuss their relation, and prove an optimality condition which may be viewed as the counterpart of what is called M-stationarity in the MPEC-field.     

Epi-convergence Properties of Smoothing by Infimal Convolution

This paper concerns smoothing by infimal convolution for two large classes of functions: convex, proper and lower semicontinous as well as for (the nonconvex class of) convex-composite functions. The smooth approximations are constructed so that they epi-converge (to the underlying nonsmooth function) and fulfill a desirable property with respect to graph convergence of the gradient mappings to the subdifferential of the original function under reasonable assumptions. The close connection between epi-convergence of the smoothing functions and coercivity properties of the smoothing kernel is established.     

Pair and singlet diffusion in a Lennard-Jones liquid

Inspired by the experimental work of Richter et al. [1], we have investigated the dynamic behaviour of pairs of particles of a Lennard-Jones liquid for four different thermodynamic states. The short and long time behaviour of dynamic correlation functions of pairs are studied and directly compared with that of single particle correlation functions. Only those relating to singlet and pair diffusion are treated.

A list of the correlation functions considered in this work is presented in the table of the Appendix.

The main results are the following:

• (i)the mean square displacement of pairs of particles departs only slightly from that of single particles (doubled);

• (ii)for long times, the mean square displacement of pairs is significantly reduced when pairs from only the first coordination shell are considered;

• (iii)in the short time region the mean square displacment of pairs resembles that of single atoms, however that of pairs being initially closer than the mean separation of particles in the liquid exhibits a small tendency to lie above the doubled one of single particles.

Our results, obtained by extensive molecular dynamics (MD) calculations, are in quantitative disagreement with results generated by other authors [3, 4], and the findings of Posch et al. [6] could not be confirmed in detail by our work.     

Metal particles on surfaces-desorption,optical spectra,and laser-induced size manipulation

Desorption induced by electronic excitation with laser light is discussed. Emphasis is placed on nonthermal desorption where surface plasma excitation in small particles precedes the rupture of the surface chemical bond. A scenario for the mechanism underlying such a process is proposed. In this context, calculations of the electronic spectra of small sodium particles are presented and the influence of different multipole orders of the collective electron oscillation, of different shapes of the clusters and of the substrate are outlined. Furthermore, manipulation of the size distribution of metal particles on supports is described as an application of the effect. This allows the preparation of very special surfaces with novel physical and chemical properties. Methods to characterize such adsorbate-substrate combinations, especially by use of the optical spectra of the particles, are also discussed. Finally, prospects for future experiments in this field are outlined.