No Arabic abstract
When a cluster or nanodroplet bears charge, its structure and thermodynamics are altered and, if the charge exceeds a certain limit, the system becomes unstable with respect to fragmentation. Some of the key results in this area were derived by Rayleigh in the nineteenth century using a continuum model of liquid droplets. Here we revisit the topic using a simple particle-based description, presenting a systematic case study of how charge affects the physical properties of a Lennard-Jones cluster composed of 309 particles. We find that the ability of the cluster to sustain charge depends on the number of particles over which the charge is distributed---a parameter not included in Rayleighs analysis. Furthermore, the cluster may fragment before the charge is strong enough to drive all charged particles to the surface. The charged particles in stable clusters are therefore likely to reside in the clusters interior even without considering solvation effects.
Using calculations from first principles, we herein consider the bond made between thiolat e with a range of different Au clusters, with a particular focus on the spin moments inv olved in each case. For odd number of gold atoms, the clusters show a spin moment of 1.~ $mu_B$. The variation of spin moment with particle size is particularly dramatic, with t he spin moment being zero for even numbers of gold atoms. This variation may be linked w ith changes in the odd-even oscillations that occur with the number of gold atoms, and is associated with the formation of a S-Au bond. This bond leads to the presence of an extra electron that is mainly sp in character in the gold part. Our results sugg est that any thiolate-induced magnetism that occurs in gold nanoparticles may be locali zed in a shell below the surface, and can be controlled by modifying the coverage of the thiolates.
A detailed simple model is applied to study a metallic cluster. It is assumed that the ions and delocalized electrons are distributed randomly throughout the cluster. The delocalized electrons are assumed to be degenerate. A spherical ball models the shape of a cluster. The energy of the microscopic electrostatic field around the ions is taken into account and calculated. It is shown in the framework of the model that the cluster is stable. Equilibrium radius of a ball and the energy of the equilibrium cluster are calculated. Bulk modulus of a cluster is calculated also.
We study the energy landscapes of particles with short-range attractive interactions as the range of the interactions increases. Starting with the set of local minima for $6leq Nleq12$ hard spheres that are sticky, i.e. they interact only when their surfaces are exactly in contact, we use numerical continuation to evolve the local minima (clusters) as the range of the potential increases, using both the Lennard-Jones and Morse families of interaction potentials. As the range increases, clusters merge, until at long ranges only one or two clusters are left. We compare clusters obtained by continuation with different potentials and find that for short and medium ranges, up to about 30% of particle diameter, the continued clusters are nearly identical, both within and across families of potentials. For longer ranges the clusters vary significantly, with more variation between families of potentials than within a family. We analyze the mechanisms behind the merge events, and find that most rearrangements occur when a pair of non-bonded particles comes within the range of the potential. An exception occurs for nonharmonic clusters, those that have a zero eigenvalue in their Hessian, which undergo a more global rearrangement.
We study the deformations of pH-responsive spherical microcapsules -- micrometer-scale liquid drops surrounded by thin, solid shells -- under the influence of electrostatic forces. When exposed to a large concentration of NaOH, the microcapsules become highly charged, and expand isotropically. We find that the extent of this expansion can be understood by coupling electrostatics with shell theory; moreover, the expansion dynamics is well described by Darcys law for fluid flow through the microcapsule shell. Unexpectedly, however, below a threshold NaOH concentration, the microcapsules begin to disintegrate, and eventually rupture; they then expand non-uniformly, ultimately forming large, jellyfish-like structures. Our results highlight the fascinating range of behaviors exhibited by pH-responsive microcapsules, driven by the interplay between electrostatic and mechanical forces.
A unique property of metal nanoclusters is the superatom shell structure of their delocalized electrons. The electronic shell levels are highly degenerate and therefore represent sharp peaks in the density of states. This can enable exceptionally strong electron pairing in certain clusters composed of tens to hundreds of atoms. In a finite system, such as a free nanocluster or a nucleus, pairing is observed most clearly via its effect on the energy spectrum of the constituent fermions. Accordingly, we performed a photoionization spectroscopy study of size-resolved aluminum nanoclusters and observed a rapid rise of the near-threshold density of states of several clusters ($Al_{37,44,66,68}$) with decreasing temperature. The characteristics of this behavior are consistent with compression of the density of states by a pairing transition into a high-temperature superconducting state with $T_c$>~100 K. This value exceeds that of bulk aluminum by two orders of magnitude. These results highlight the potential of novel pairing effects in size-quantized systems and the possibility to attain even higher critical temperatures by optimizing the particles size and composition. As a new class of high-temperature superconductors, such metal nanocluster particles are promising building blocks for high-$T_c$ materials, devices, and networks.