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Molecular dynamics (MD) of the Lennard-Jones cluster in the environment of supersaturated vapor at fixed temperature and density is used for the investigation of nonisothermal nucleation. The results allow one to single out different processes occurring at different time scales, the Ornstein–Uhlenbeck fluctuations at the short time scale and a combination of slow diffusion and drift of the fluctuation packet that represents a cluster, at the long time scale. The multiscale approach is developed, in which a separate treatment of different time scales makes it possible to consider strongly correlated cluster size and temperature. This reduces the nonisothermal cluster evolution to a one-dimensional problem. The fluctuation packet drift velocity and diffusivity are calculated based on the cluster microscopic thermophysical parameters determined in this work from MD data for isothermal clusters. The proposed approach is consistent with the results of our MD simulation. [ABSTRACT FROM AUTHOR]

A molecular dynamics simulation of a system of massive charged particles on a compensating homogeneous background confined by a spherical surface has been carried out. A crystallized cluster is a set of nested spherical shells of almost the same structure and a core. It is shown that cluster melting is a combination of shell and core melting. It is found that the values of the Coulomb coupling parameter Γ corresponding to these two types of melting do not depend on the cluster size. Methods for determining Γ based on the Wigner–Seitz cell model are discussed. It is shown that the estimate based on the root-mean-square deviation of a particle from the center of its cell is unreliable due to the self-diffusion of particles. A relation is proposed that defines Γ in terms of the root-mean-square velocity and acceleration of the particle and does not include the root-mean-square deviation of the particle from its average position. It is shown that this relation is satisfied with high accuracy not only for the crystallized, but also for the liquid state. Thus, it has been demonstrated that the Wigner–Seitz cell model is applicable to the strongly inhomogeneous system under consideration. [ABSTRACT FROM AUTHOR]

Clusters of atoms in dense gold vapor are studied via atomistic simulation with the classical molecular dynamics method. For this purpose, we develop a new embedded atom model potential applicable to the lightest gold clusters and to the bulk gold. Simulation provides the equilibrium vapor phases at several subcritical temperatures, in which the clusters comprising up to 26 atoms are detected and analyzed. The cluster size distributions are found to match both the two-parameter model and the classical nucleation theory with the Tolman correction. For the gold liquid–vapor interface, the ratio of the Tolman length to the radius of a molecular cell in the liquid amounts to ∼0.16, almost exactly the value at which both models are identical. It is demonstrated that the lightest clusters have the chain-like structure, which is close to the freely jointed chain. Thus, the smallest clusters can be treated as the quasi-fractals with the fractal dimensionality close to two. Our analysis indicates that the cluster structural transition from the solid-like to chain-like geometry occurs in a wide temperature range around 2500 K. [ABSTRACT FROM AUTHOR]

The vapor-liquid nucleation in a dense Lennard-Jones system is studied analytically and numerically. A solution of the nucleation kinetic equations, which includes the elementary processes of condensation/evaporation involving the lightest clusters, is obtained, and the nucleation rate is calculated. Based on the equation of state for the cluster vapor, the pre-exponential factor is obtained. The latter diverges as a spinodal is reached, which results in the nucleation enhancement. The work of critical cluster formation is calculated using the previously developed two-parameter model (TPM) of small clusters. A simple expression for the nucleation rate is deduced and it is shown that the work of cluster formation is reduced for a dense vapor. This results in the nucleation enhancement as well. To verify the TPM, a simulation is performed that mimics a steady-state nucleation experiments in the thermal diffusion cloud chamber. The nucleating vapor with and without a carrier gas is simulated using two different thermostats for the monomers and clusters. The TPM proves to match the simulation results of this work and of other studies. [ABSTRACT FROM AUTHOR]

We explore thermodynamic properties of a vapor in the range of state parameters where the contribution to thermodynamic functions from bound states of atoms (clusters) dominates over the interaction between the components of the vapor in free states. The clusters are assumed to be light and sufficiently "hot" for the number of bonds to be minimized. W e use the technique of calculation of the cluster partition function for the cluster with a minimum number of interatomic bonds to calculate the caloric properties (heat capacity and velocity of sound) for an ideal mixture of the lightest clusters. The problem proves to be exactly solvable and resulting formulas are functions solely of the equilibrium constant of the dimer formation. These formulas ensure a satisfactory correlation with the reference data for the vapors of cesium, mercury, and argon up to moderate densities in both the sub- and supercritical regions. For cesium, we extend the model to the densities close to the critical one by inclusion of the clusters of arbitrary size. Knowledge of the cluster composition of the cesium vapor makes it possible to treat nonequilibrium phenomena such as nucleation of the supersaturated vapor, for which the effect of the cluster structural transition is likely to be significant. [ABSTRACT FROM AUTHOR]

Analysis of surface fluctuation spectra is performed for a large cluster of particles interacting via a sum of the short-range Lennard-Jones potential and long-range ±1/r potential, where the positive sign corresponds to the gravity, and negative corresponds to the electrostatic interaction. The spectral amplitudes of thermally driven capillary modes in a self-consistent field induced by cluster particles including the modes with no axial symmetry are derived in the approximation of small amplitudes. It is demonstrated that within used approximation, the surface tension is independent of the field strength. The low wave vector amplitudes are damped by attracting field that compresses the cluster and magnified by repulsing field leading to cluster fission. The fission threshold is found to be different from that found by Bohr and Wheeler and Frenkel due to the replacement of the ordinary surface tension by the bare one. Molecular dynamics study of a cluster with the long-range interaction in the vapor environment is performed using a novel integrator for a multiscale system. Simulation scheme implies rotation of the long-range components of forces acting on cluster particles thus vanishing an artificial torque. Simulation results justify theoretical conclusion of modes damping and independence of the surface tension of the field strength. Fission threshold evaluated from simulation data is in a good agreement with theory. [ABSTRACT FROM AUTHOR]

Spectra of the cluster surface equilibrium fluctuations are treated by decomposition into the bulk and net capillary ones. The bulk fluctuations without capillary ones are simulated by the surface of a cluster truncated by a sphere. The bulk fluctuation spectrum is shown to be generated primarily by the discontinuity in the spatial distribution of cluster internal particles. The net capillary fluctuation slice spectrum is obtained in molecular dynamics simulation by subtraction of the bulk fluctuation spectrum from the total one. This net spectrum is in the best agreement with a theoretical estimation if we assume the intrinsic surface tension to be independent of the wave number. The wave number cutoff is brought in balance with the intrinsic surface tension and excess surface area induced by the capillary fluctuations. It is shown that the ratio of the ordinary surface tension to the intrinsic one can be considered as a universal constant independent of the temperature and cluster size. [ABSTRACT FROM AUTHOR]

Classification of cluster particles is proposed that introduces three particle types: the internal particles, surface particles, and virtual chains of particles. Thermal fluctuations of a surface passing through the surface particles of a Lennard-Jones liquid cluster are studied using a molecular dynamics simulation. It is shown that for large clusters, the Fourier spectral amplitude of these fluctuations decays faster than 1/q, where q is the wave number. The frequency Fourier spectrum shows an overdamped system behavior, which is the evidence for the absence of thermal capillary waves for clusters comprising less than 105 particles. The time-averaged cluster density profile is given by an error function with the width parameter diverging as the logarithm of the cluster size. [ABSTRACT FROM AUTHOR]

Behavior of an argonlike cluster in supersaturated vapor at constant temperature and pressure is simulated. In contrast to the results of conventional microcanonical ensemble simulations, instability of cluster size is observed (unlimited growth or complete evaporation). This defines cluster critical size, which is noticeably larger than that predicted by the classical nucleation theory. Analysis of cluster collective vibrational spectra shows that its evaporation is intimately connected with spontaneous emergence of the lowest modes of breathing vibrations. The cluster phonon spectrum resembles that of a strange attractor. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]

A size-corrected thermodynamic model for clusters is proposed which implies that cluster chemical potential is a linear function of the number of molecules at its surface and the total number of molecules. The model is free from the introduction of the surface tension for small clusters and therefore has no limitation in this size range. The expressions for homogeneous nucleation rates have been obtained in the approximations of small and large critical sizes. Calculated nucleation rates are slightly lower than predicted by the classical theory for water vapor and much higher for mercury vapor, in agreement with the experiments. [ABSTRACT FROM AUTHOR]