Dynamics Simulations Of Homogeneous Nucleation Research Articles

Molecular dynamics simulation of homogeneous nucleation of melting in superheated sodium crystal

The melting process and nucleation behaviour of sodium (Na) crystals are crucial for the frozen start-up of high-temperature sodium heat pipes and the working performance of molten sodium batteries. Equilibrium melting and the homogeneous nucleation of melting in superheated Na crystal are studied by molecular dynamics simulation. The thermodynamic properties and nucleation of Na crystal during the heating process are investigated by the characterization of the density, radial distribution function (RDF), self-diffusion coefficient (D), nucleation rate (Ihom), etc. Firstly, the equilibrium melting of Na crystal is simulated and verified by the single-phase method. Results show that Na's equilibrium melting temperature, densities, and RDF simulated match well with experimental values, demonstrating that the EAM/FS potential is suitable for studying the melting processes of Na crystal. Secondly, the calculated D of liquid Na increases approximately linearly with rising temperature within 440 K∼540 K and fits with experimental data well. The activation energy for the diffusion of Na obtained by linear fitting is 1.6406·10-20 J, which agrees well with the observed values. Finally, the homogeneous nucleation of melting in superheated Na crystal is analyzed. It is found that the Ihom of melting in superheated Na crystal rises exponentially with increasing temperature, which is consistent with the prediction in literature. The kinetic stability limit of superheated Na crystal is 468.3 K, and the relation between the Ihom of melting in superheated Na crystal and temperature is given. The physical properties and nucleation theory of Na crystal simulated during the melting can provide theoretical support for sodium's heat and mass transfer-related applications, such as sodium heat pipes and sodium batteries.

Molecular Dynamics Simulation of Homogeneous Nucleation and Growth of Supercooled Al Liquid

Molecular dynamics simulation is used to study the spontaneous nucleation and solidification of Al liquid. According to the mean first-passage time (MFPT), the critical crystal nucleus size at 31.6% undercooling is 152 atoms, the nucleation rate is [Formula: see text][Formula: see text]m[Formula: see text][Formula: see text]s[Formula: see text]. The nucleation rate obtained by the survival probability (SP) is [Formula: see text][Formula: see text]m[Formula: see text][Formula: see text]s[Formula: see text], which is very consistent with the result obtained by MFPT. Using Johnson–Mehl–Avrami (JMA) law to analyze the growth of the two extreme conditions in the experiment, the system with the smallest average atomic volume (Run38) grows faster than the system with the largest volume (Run73). In terms of microstructure, Run38 is a lamellar (LAM) structure, and Run73 is a complex polycrystalline structure accompanied by five-fold twinning (FFT). The shapes of clusters in a given range (5–10,000 atoms) during solidification in 100 experiments were counted. The results show that no clusters are perfectly spherical, but ellipsoids are of different shapes, and the larger the ellipsoid size, the closer to a spherical shape.

Molecular dynamics simulations of homogeneous nucleation of liquid phase in highly supersaturated propylene glycol vapors

The homogeneous nucleation rate of the liquid phase from a supersaturated propylene glycol vapor is a key factor in aerosol formation from condensation aerosol generators. The droplet nucleation rate is difficult to measure experimentally at high supersaturations. This paper demonstrates the feasibility of using classical Molecular Dynamics (MD) simulations to describe the nucleation of propylene glycol from the vapor phase in air at 320 and 343 K. After an initial induction period, nucleation was observed in many of the scenarios studied here. The classical nucleation theory underestimates the nucleation rate compared to the MD simulation results at high supersaturations. However, a kinetic model that assumed no free energy barrier to nucleation had better agreement with the MD predictions at extremely high supersaturations. For systems where a quasi-steady state was reached during the simulation, it is possible to determine the nucleation free energy as a function of cluster size. From this analysis it is found that the MD simulations predict over a factor of two larger critical clusters and about 50% higher free energy barriers than the classical nucleation theory.

Large-Scale Molecular Dynamics Simulations of Homogeneous Nucleation of Pure Aluminium

Despite the continuous and remarkable development of experimental techniques for the investigation of microstructures and the growth of nuclei during the solidification of metals, there are still unknown territories around this topic. The solidification in nanoscale can be effectively investigated by means of molecular dynamics (MD) simulations which can provide a deep insight into the mechanisms of the formation of nuclei and the induced crystal structures. In this study, MD simulations were performed to investigate the solidification of pure Aluminium and the effects of the cooling rate on the final properties of the solidified material. A large number of Aluminium atoms were used in order to investigate the grain growth over time and the formation of stacking faults during solidification. The number of face-centred cubic (FCC), hexagonal close-packed (HCP) and body-centred cubic (BCC) was recorded during the evolution of the process to illustrate the nanoscale mechanisms initiating solidification. The current investigation also focuses on the exothermic nature of the solidification process which has been effectively captured by means of MD simulations using 3 dimensional representations of the kinetic energy across the simulation domain.

Molecular dynamics simulation of homogeneous nucleation of supersaturated potassium chloride (KCl) in aqueous solutions

Molecular dynamics (MD) simulation is used to investigate the mechanism of crystal nucleation of potassium chloride (KCl) in a supersaturated aqueous solution at 293 K and 1 atm.

Molecular dynamics simulation of homogeneous nucleation in a superheated Lennard-Jones crystal

We present the results of a molecular dynamics study of homogeneous nucleation of liquid drops in a superheated Lennard-Jones (LJ) crystal at positive and negative pressures. The mean lifetime method has been used to determine the nucleation rate, calculate the Zeldovich nonequilibrium factor and the diffusion coefficient of nuclei, and determine the contribution of elastic stresses to the work of formation of a critical nucleus. The data obtained are compared with classical nucleation theory (CNT). A considerable discrepancy between data of MD simulation and CNT (up to 70 orders in the nucleation rate) has been established. With a satisfactory agreement between theory and simulation in the rate of the nucleus transition through the critical size, an essential discrepancy is observed in the work of formation of a critical nucleus. The neglect of elastic stresses in the nucleation work improves the agreement between the results of theory and simulation. The effect of the size dependence of the surface free energy of a critical nucleus on the work of its formation is estimated.

Suppression of homogeneous crystal nucleation of the NiAl intermetallic by a composition gradient: A molecular dynamics study

Molecular dynamics simulations of homogeneous nucleation of the NiAl intermetallic phase from a liquid solution on cooling indicate that this phase transformation is suppressed in the presence of a composition gradient. A simulation method is designed to generate a sustaining composition gradient at the interface between two materials. As the composition gradient increases, the nucleation energy barrier rises, the critical nucleus size increases, and the nucleus shape develops an increasing asymmetry. A polymorphic nucleation model for a disk-shaped nucleus that incorporates the composition dependence of interfacial free energies was observed to describe the atomic-scale details of the simulation well. Critical nuclei shapes and volumes predicted by the model match with those appearing in the molecular dynamics simulations.

Heterogeneity in homogeneous nucleation from billion-atom molecular dynamics simulation of solidification of pure metal

Can completely homogeneous nucleation occur? Large scale molecular dynamics simulations performed on a graphics-processing-unit rich supercomputer can shed light on this long-standing issue. Here, a billion-atom molecular dynamics simulation of homogeneous nucleation from an undercooled iron melt reveals that some satellite-like small grains surrounding previously formed large grains exist in the middle of the nucleation process, which are not distributed uniformly. At the same time, grains with a twin boundary are formed by heterogeneous nucleation from the surface of the previously formed grains. The local heterogeneity in the distribution of grains is caused by the local accumulation of the icosahedral structure in the undercooled melt near the previously formed grains. This insight is mainly attributable to the multi-graphics processing unit parallel computation combined with the rapid progress in high-performance computational environments.

Free energy of cluster formation and a new scaling relation for the nucleation rate.

Recent very large molecular dynamics simulations of homogeneous nucleation with (1 - 8) × 10(9) Lennard-Jones atoms [J. Diemand, R. Angélil, K. K. Tanaka, and H. Tanaka, J. Chem. Phys. 139, 074309 (2013)] allow us to accurately determine the formation free energy of clusters over a wide range of cluster sizes. This is now possible because such large simulations allow for very precise measurements of the cluster size distribution in the steady state nucleation regime. The peaks of the free energy curves give critical cluster sizes, which agree well with independent estimates based on the nucleation theorem. Using these results, we derive an analytical formula and a new scaling relation for nucleation rates: ln J'/η is scaled by ln S/η, where the supersaturation ratio is S, η is the dimensionless surface energy, and J(') is a dimensionless nucleation rate. This relation can be derived using the free energy of cluster formation at equilibrium which corresponds to the surface energy required to form the vapor-liquid interface. At low temperatures (below the triple point), we find that the surface energy divided by that of the classical nucleation theory does not depend on temperature, which leads to the scaling relation and implies a constant, positive Tolman length equal to half of the mean inter-particle separation in the liquid phase.

Large scale molecular dynamics simulations of homogeneous nucleation

We present results from large-scale molecular dynamics (MD) simulations of homogeneous vapor-to-liquid nucleation. The simulations contain between 1 × 10(9) and 8 × 10(9) Lennard-Jones (LJ) atoms, covering up to 1.2 μs (56 × 10(6) time-steps). They cover a wide range of supersaturation ratios, S ≃ 1.55-10(4), and temperatures from kT = 0.3 to 1.0ε (where ε is the depth of the LJ potential, and k is the Boltzmann constant). We have resolved nucleation rates as low as 10(17) cm(-3) s(-1) (in the argon system), and critical cluster sizes as large as 100 atoms. Recent argon nucleation experiments probe nucleation rates in an overlapping range, making the first direct comparison between laboratory experiments and molecular dynamics simulations possible: We find very good agreement within the uncertainties, which are mainly due to the extrapolations of argon and LJ saturation curves to very low temperatures. The self-consistent, modified classical nucleation model of Girshick and Chiu [J. Chem. Phys. 93, 1273 (1990)] underestimates the nucleation rates by up to 9 orders of magnitudes at low temperatures, and at kT = 1.0ε it overestimates them by up to 10(5). The predictions from a semi-phenomenological model by Laaksonen et al. [Phys. Rev. E 49, 5517 (1994)] are much closer to our MD results, but still differ by factors of up to 10(4) in some cases. At low temperatures, the classical theory predicts critical clusters sizes, which match the simulation results (using the first nucleation theorem) quite well, while the semi-phenomenological model slightly underestimates them. At kT = 1.0ε, the critical sizes from both models are clearly too small. In our simulations the growth rates per encounter, which are often taken to be unity in nucleation models, lie in a range from 0.05 to 0.24. We devise a new, empirical nucleation model based on free energy functions derived from subcritical cluster abundances, and find that it performs well in estimating nucleation rates.

Homogeneous Nucleation of Methane Hydrate in Microsecond Molecular Dynamics Simulations.

We report atomistically detailed molecular dynamics simulations of homogeneous nucleation of methane hydrate in bulk aqueous phase in the absence of any interface. Subcritical clusters of water and methane molecules are formed in the initial segment of the simulations, which then aggregate to give the critical hydrate nucleus. This occurs over time scales of several hundred nanoseconds, indicating that the formation and aggregation of subcritical clusters can contribute significantly to the overall rate of hydrate nucleation. The clusters have elements of sI hydrate structure, such as 5(12) and 5(12)6(2) cages as well as other uncommon 5(12)6(3) and 5(12)6(4) cages, but do not possess long-range order. Clusters are dynamic in nature and undergo continuous structural rearrangements.

Molecular dynamics simulation of homogeneous nucleation of KBr cluster

We perform molecular dynamics simulations to study the homogeneous nucleation in the freezing of molten potassium bromide clusters. The nucleation rates tend to decrease with increasing cluster size and temperature. The solid–liquid interfacial free energy σ sl of 42.4–52.3 mJ/m 2 is close to the values predicted by Turnbull's relation and comparable to the experimental observation by Buckle and Ubbelohde. It is interesting to find that there is no cluster size effect on the critical nucleus size. Critical nucleus sizes inferred from classical nucleation theory are of 6.5–20.7 K +Br − ionic pairs in the temperature range of 400–600 K. The critical nucleus size at bulk MD freezing temperature obtained by extrapolation is about 45 K +Br − ionic pairs, which is comparable to the experimental value of NaCl.

Molecular dynamics simulation of homogeneous nucleation in supersaturated water vapor

Molecular dynamics computer simulation of a water system was carried out to investigate the dynamics of vapor phase homogeneous nucleation at 350 K under super saturation ratio 14.6. To control the system temperature, 5000 target particles were mixed with 5000 carrier gas particles. The observed nucleation rate is three orders of magnitude smaller than prediction of a classical nucleation theory. From the cluster size distribution in steady state region, the free energy of cluster formation is estimated, which diminishes the difference between the theoretical prediction and the simulational result concerning the nucleation rate.