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Water freezing, initiated by ice nucleation, occurs widely in nature, ranging from cellular to global phenomena. Ice nucleation has been experimentally proven to require the formation of a critical ice nucleus, consistent with classical nucleation theory (CNT). However, the accuracy of CNT quantitative predictions of critical cluster sizes and nucleation rates has never been verified experimentally. In this study, we circumvent this difficulty by using molecular dynamics (MD) simulation. The physical properties of water/ice for CNT predictions, including density, chemical potential difference, and diffusion coefficient, are independently obtained using MD simulation, whereas the calculation of interfacial free energy is based on thermodynamic assumptions of CNT, including capillarity approximation among others. The CNT predictions are compared to the MD evaluations of brute-force simulations and forward flux sampling methods. We find that the CNT and MD predicted critical cluster sizes are consistent, and the CNT predicted nucleation rates are higher than the MD predicted values within three orders of magnitude. We also find that the ice crystallized from supercooled water is stacking-disordered ice with a stacking of cubic and hexagonal ices in four representative types of stacking. The prediction discrepancies in nucleation rate mainly arise from the stacking-disordered ice structure, the asphericity of ice cluster, the uncertainty of ice–water interfacial free energy, and the kinetic attachment rate. Our study establishes a relation between CNT and MD to predict homogeneous ice nucleation. [ABSTRACT FROM AUTHOR]

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]

The crystallization of complex, concentrated alloys can result in atomic-level short-range order, composition gradients, and phase separation. These features govern the properties of the resulting alloy. While nucleation and growth in single-element metals are well understood, several open questions remain regarding the crystallization of multi-principal component alloys. We use molecular dynamics to model the crystallization of a five-element, equiatomic alloy modeled after CoCrCuFeNi upon cooling from the melt. Stochastic, homogeneous nucleation results in nuclei with a biased composition distribution, rich in Fe and Co. This deviation from the random sampling of the overall composition is driven by the internal energy and affects nuclei of a wide range of sizes, from tens of atoms all the way to super-critical sizes. This results in short-range order and compositional gradients at nanometer scales. [ABSTRACT FROM AUTHOR]

The large discrepancy among the nucleation kinetics extracted from experimental measurements and computer simulations and the prediction of the classical nucleation theory (CNT) has stimulated intense arguments about its origin in the past decades, which is crucially relevant to the validity of the CNT. In this paper, we investigate the atomistic mechanism of the nucleation in liquid Al in contact with amorphous substrates with atomic-level smooth/rough surfaces, using molecular dynamics (MD) simulations. This study reveals that the slightly distorted local fcc/hcp structures in amorphous substrates with smooth surfaces can promote heterogeneous nucleation through a structural templating mechanism, and on the other hand, homogeneous nucleation will occur at a larger undercooling through a fluctuation mechanism if the surface is rough. Thus, some impurities, previously thought to be impotent, could be activated in the homogeneous nucleation experiments. We further find that the initial growth of the nucleus on smooth surfaces of amorphous substrates is one order of magnitude faster than that in homogeneous nucleation. Both these factors could significantly contribute to the discrepancy in the nucleation kinetics. This study is also supported by a recent study of the synthesis of high-entropy alloy nanoparticles assisted with the liquid metal Ga [Cao et al., Nature 619, 73 (2023)]. In this study, we established that the boundary existed between homogeneous and heterogeneous nucleation, i.e., the structural templating is a general mechanism for heterogeneous nucleation, and in its absence, homogeneous nucleation will occur through the fluctuation mechanism. This study provides an in-depth understanding of the nucleation theory and experiments. [ABSTRACT FROM AUTHOR]

Understanding the ice nucleation mechanism in the catalyst layers (CLs) of proton exchange membrane (PEM) fuel cells and inhibiting icing by designing the CLs can optimize the cold start strategies, which can enhance the performance of PEM fuel cells. Herein, mitigating the structural matching and templating effects by adjusting the surface morphology and wettability can inhibit icing on the platinum (Pt) catalyst surface effectively. The Pt(211) surface can inhibit icing because the atomic spacing of (211) crystalline surface is much larger than the characteristic distance of ice crystal, thereby mitigating the structural matching effects. A water overlayer on the Pt surface induced by the strong attraction of Pt can act as a template for ice layers and plays an important role in the icing process. Buckling of water overlayer due to the larger atomic spacing of (211) crystalline surface mitigates the templating effect and inhibits icing. Moreover, the water overlayer on the hydrophobic Pt(211) surface with fewer water molecules also mitigates the templating effect, which makes ice nucleation more difficult than homogeneous nucleation. These findings reveal the ice nucleation mechanisms on the Pt catalyst surface from the molecular level and are valuable for catalyst designs to inhibit icing in CL. [ABSTRACT FROM AUTHOR]

Nucleation is a fundamental and general process at the initial stage of first-order phase transition. Although various models based on the classical nucleation theory (CNT) have been proposed to explain the energetics and kinetics of nucleation, detailed understanding at nanoscale is still required. Here, in view of the homogeneous bubble nucleation, we focus on cavity formation, in which evaluation of the size dependence of free energy change is the key issue. We propose the application of a formula in stochastic thermodynamics, the Jarzynski equality, for data analysis of molecular dynamics (MD) simulation to evaluate the free energy of cavity formation. As a test case, we performed a series of MD simulations with a Lennard-Jones (LJ) fluid system. By applying an external spherical force field to equilibrated LJ liquid, we evaluated the free energy change during cavity growth as the Jarzynski's ensemble average of required works. A fairly smooth free energy curve was obtained as a function of bubble radius in metastable liquid of mildly negative pressure conditions. [ABSTRACT FROM AUTHOR]

Methane hydrates are important from a scientific and industrial perspective, and form by nucleation and growth from a supersaturated aqueous solution of methane. Molecular simulation is able to shed light on the process of homogeneous nucleation of hydrates, using straightforward molecular dynamics or rare event enhanced sampling techniques with atomistic and coarse grained force fields. In our previous work [Arjun, T. A. Berendsen, and P. G. Bolhuis, Proc. Natl. Acad. Sci. U. S. A. 116, 19305 (2019)], we performed transition path sampling (TPS) simulations using all atom force fields under moderate driving forces at high pressure, which enabled unbiased atomistic insight into the formation of methane hydrates. The supersaturation in these simulations was influenced by the Laplace pressure induced by the spherical gas reservoir. Here, we investigate the effect of removing this influence. Focusing on the supercooled, supersaturated regime to keep the system size tractable, our TPS simulations indicate that nuclei form amorphous structures below roughly 260 K and crystalline sI structures above 260 K. For these temperatures, the average transition path lengths are significantly longer than in our previous study, pushing the boundaries of what can be achieved with TPS. The temperature to observe a critical nucleus of certain size was roughly 20 K lower compared to a spherical reservoir due to the lower concentration of methane in the solution, yielding a reduced driving force. We analyze the TPS results using a model based on classical nucleation theory. The corresponding free energy barriers are estimated and found to be consistent with previous predictions, thus adding to the overall picture of the hydrate formation process. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulation was applied to investigate the interaction between precipitate and 10 1 ¯ 2 twin in Mg-Al alloy in this work. Three sets of simulation including twin nucleation, propagation and growth affected by precipitate were performed. The results show the introduction of precipitate has little effect on neither the homogeneous twin nucleation at random site inside the grain nor the heterogeneous nucleation at grain boundary. During twin propagation, the blocking effect of precipitate to the twin tip depends on its size. The twin tip can bypass the precipitate when the precipitate is not long enough. When the length of precipitate is much larger than the thickness of twin, the twin tip will be completely blocked by the precipitate with elastic bending occurring at the junction. During the twin growth, it is found that the precipitate plays not only an obstacle but a source for the twinning dislocations gliding along the twin boundary. The blocking effect of precipitate on twin growth shows a size effect. The influences of width and thickness on precipitation hardening are significantly greater than that of length. [ABSTRACT FROM AUTHOR]

Polarization switching in ferroelectric hysteresis of BaTiO3 proceeds by localized nucleation and subsequent growth of domains of reverse polarization. While this process is driven by the applied electric field, thermal activation can play an important role in domain nucleation. As a consequence of the stochastic nature of thermal activation, coercive fields in small systems exhibit a significant scatter. It is demonstrated that the statistics of coercive fields observed in molecular dynamics simulations is consistent with the statistical distribution expected for field-assisted thermally activated nucleation of reverse polarization domains. The excellent quantitative agreement between the simulation data and the theory of thermally activated processes provides strong evidence that polarization switching occurs by nucleation-and-growth rather than loss of the local minimum of the Gibbs free energy function. In a pristine crystal, switching is controlled by the field at which thermal fluctuations can create a critical nucleus in the bulk (homogeneous nucleation). The analysis of crystals with various vacancy-type defects demonstrates that such defects may enable heterogeneous nucleation at reduced fields. In both cases, the statistical analysis gives access to the respective activation energies, their field dependence, and the sizes of the critical nuclei. [ABSTRACT FROM AUTHOR]

Semicrystalline polymers are ubiquitous, yet despite their fundamental and industrial importance, the theory of homogeneous nucleation from a melt remains a subject of debate. A key component of the controversy is that polymer crystallization is a non-equilibrium process, making it difficult to distinguish between effects that are purely kinetic and those that arise from the underlying thermodynamics. Due to computational cost constraints, simulations of polymer crystallization typically employ non-equilibrium molecular dynamics techniques with large degrees of undercooling that further exacerbate the coupling between thermodynamics and kinetics. In a departure from this approach, in this study, we isolate the near-equilibrium nucleation behavior of a simple model of a melt of short, semiflexible oligomers. We employ several Monte Carlo methods and compute a phase diagram in the temperature–density plane along with two-dimensional free energy landscapes (FELs) that characterize the nucleation behavior. The phase diagram shows the existence of ordered nematic and crystalline phases in addition to the disordered melt phase. The minimum free energy path in the FEL for the melt–crystal transition shows a cooperative transition, where nematic order and monomer positional order move in tandem as the system crystallizes. This near-equilibrium phase transition mechanism broadly agrees with recent evidence that polymer stiffness plays an important role in crystallization but differs in the specifics of the mechanism from several recent theories. We conclude that the computation of multidimensional FELs for models that are larger and more fine-grained will be important for evaluating and refining theories of homogeneous nucleation for polymer crystallization. [ABSTRACT FROM AUTHOR]

High energy ball milling of metallic powders leads to high reactivity in the milled mixture. The reaction is often faster and starts at a lower temperature. However, the mechanisms responsible for this high reactivity are not yet completely understood. The aim of this study is to evaluate one of the possible activating factors of this heightened reactivity: nano-scale mixing of the reagents. Molecular dynamics was used to analyze the role of an amorphous Ni–Al mixing layer, mimicking the powder microstructure after milling, between two Ni layers. The impact of temperature and stoichiometry was investigated in relation to the formation of the B 2 -NiAl intermetallic compound. At low temperatures, pre-mixing does not seem to slow down the diffusion of Ni atoms in an amorphous Al region. Homogeneous nucleation was observed in this peculiar milled microstructure. These two phenomena explain why the nano-scale mixing observed experimentally after high energy milling is indeed an activating factor in the reactivity of metallic systems such as Ni–Al. [ABSTRACT FROM AUTHOR]

Hydrodynamic flow can have complex and far-reaching consequences on the rate of homogeneous nucleation. We present a general formalism for calculating the nucleation rates of simply sheared systems. We have derived an extension to the conventional Classical Nucleation Theory, explicitly embodying the shear rate. Seeded molecular dynamics simulations form the backbone of our approach. The framework can be used for moderate supercooling, at which temperatures brute-force methods are practically infeasible. The competing energetic and kinetic effects of shear arise naturally from the equations. We show how the theory can be used to identify shear regimes of ice nucleation behavior for the mW water model, unifying disparate trends reported in the literature. At each temperature, we define a crossover shear rate in the limit of 1000 s−1–10 000 s−1, beyond which the nucleation rate increases steadily up to a maximum, at the optimal shear rate. For 235 K, 240 K, 255 K, and 260 K, the optimal shear rates are in the range of ≈106 s−1–107 s−1. For very high shear rates beyond 108 s−1, nucleation is strongly inhibited. Our results indicate that the optimal shear rates have a non-monotonic dependence on temperature. [ABSTRACT FROM AUTHOR]

In the molecular dynamics study of short-pulsed laser processing of semiconductors, potential models capable of describing the atomistic behavior during high electronic excitations is the most critical issue at the current stage. This study of the molecular dynamics adopts the Tersoff-potential model to analyze the ultrafast laser processing of silicon. The model was modified to include electronic excitation effects by reducing the attraction of the antibonding state by half. It offers an excellent description of the experimental behavior during nonthermal melting. Subpicosecond melting is achieved above certain threshold levels of superheating and carrier density as required in experiments. Energy conservation is demonstrated with a bandgap energy of the order obtained in experiments. The modification of the potential mimics an absorption of bandgap energy and a subsequent lattice heating on a time scale within 0.3 ps. The melting kinetics establishes a correlation between nonthermal melting and thermal bulk melting. For superheating of less than two, the electronic melting of bond softening proceeds via homogeneous nucleation. The associated thermal theory, corrected with a limit on the nucleus radius to bond length, is still valid for the higher superheating regime. The original Tersoff model shows that this superheating by a factor of two is isothermal for spallation—the lowest-energy ablative mechanism. Its proximity to the evaporating point suggests the role of thermal boiling during spallation. [ABSTRACT FROM AUTHOR]

Effects of different pressures on the isothermal-solidification process of pure Al were studied by molecular dynamics (MD) simulation using the embedded-atom method (EAM). Al was first subjected to a rapid-cooling process, and then it was annealed under different pressures conditions. Mean first-passage times (MFPT) method, Johnson-Mehl-Avrami (JMA) law, and X-ray diffraction (XRD) simulation analysis method were used to qualify the solidification- kinetic processing. Nucleation rate, critical-nucleus size, Avrami exponent, growth exponent, and crystallite size were calculated. Results show that the nucleation rate increases as the pressure increases. The change of critical-nucleation size is not obvious as the pressure increases. With the pressure increasing, growth exponent decreases, indicative of decreased grain-growth rate. It was also found that with the pressure increasing, the Avrami exponent decreases, indicating that the increased pressure has an effect on growth modes during solidification, which changes from three-dimensional growth to one-dimensional growth. Results of XRD simulation shows that with pressure increasing, crystallite size decreases. [ABSTRACT FROM AUTHOR]

• An atomistically informed dislocation plasticity model is developed for HMX. • Physical dependent dislocation mechanisms under pore collapse are evaluated. • Strong pressure-dependent homogeneous nucleation dominates the collapse transition. • Pore collapse measures are compared in different strength models. • Heating mechanisms inducing hotspots are quantified. Pore collapse induced hotspot formation is a key mechanism for initiating detonation of shocked high explosives. Accurate continuum models that faithfully capture the pore collapse dynamics and resulting hotspot temperatures for multiscale initiation of high explosive are still lacking. Here, an atomistically informed dislocation plasticity model is developed for cyclotetramethylene tetranitramine (HMX), which includes nonlinear thermoelasticity, pressure-dependent and temperature-dependent dislocation motion and homogeneous dislocation nucleation, and new melting criteria. Nanoscale pore collapse simulations based on the proposed model could well reproduce the pore collapse transition from a strength-dominated regime to a hydrodynamic regime observed in molecular dynamics results. During the pore collapse transition, dislocation motion and dislocation generation induced plasticity is decoupled and evaluated. It indicates that the homogeneous dislocation nucleation suppresses the dislocation motion. Through linkage analysis of dislocation physical quantity histories of tracer particles, this work clarifies the interplay between physical dependences and dislocation mechanisms on pore collapse behaviors for the first time. The results reveal that the transition of pore collapse regime emerges from the strong pressure-dependent homogeneous dislocation nucleation. In addition, the pore collapse responses and energy localizations of the proposed model are further compared with different strength models to prove the importance of pressure dependence and homogeneous dislocation nucleation on pore collapse behaviors. Based on the simulations of pore collapse, the potential heat sources are quantified to provide a physical understanding of hotspot formation mechanisms. The present work demonstrates a key step in multiscale modeling of high explosive initiation in that atomistic simulation results are directly used to guide and refine the mesoscale model of energetic crystal used in the continuum. [Display omitted] [ABSTRACT FROM AUTHOR]

Facing the huge gap between the growing CO 2 emissions and net-zero emissions target to mitigate global warming, the long-term storage of excess CO 2 becomes an intractable issue. Sequestering CO 2 in the oceans as clathrate hydrates is a promising solution. Many unanswered questions still exist at the molecular level regarding how ions in seawater kinetically affect the formation of CO 2 hydrates, particularly the dual effect: as the concentration rises, salt ions shift from being a promoter of hydrate formation to becoming an inhibitor. Herein, we report the homogeneous nucleation process of CO 2 hydrates in saline solutions via molecular dynamics simulations. Consistent with experimental findings, our results show that nucleation is promoted within certain salt concentration ranges; however, the evidence suggests that ions do not act as nucleation sites. Multiple ion-induced variations in the aqueous phase are analyzed, including changes in the mobility, structure, and CO 2 solubility. We find that the presence of ions strengthens the hydrophobic interactions among the dissolved CO 2 molecules, which are associated with the salting-out phenomenon, accounting for the promoting effect of salts at low concentrations. However, as the salt concentration increases, this advantage is offset, leading to the inhibiting effect at high salt concentrations. We demonstrate that anions are inevitably involved in the construction of the solid hydrate phase. Their presence disrupts the native tetrahedral connectivity of water molecules and imparts negative charges to the solid phase, thereby attracting cations. In addition to advancing our understanding of the intricate interactions among water, guest, and additive molecules to germinate ordered solid structures, these findings can accelerate the development and utilization of sustainable hydrate-based applications. [Display omitted] • Molecular resolution into CO 2 hydrate spontaneous nucleation in saline solution. • Concentration-dependent dual effect of ions on the formation of CO 2 hydrate. • A new method for tracking hydrate nucleation process. • Ions enhance the hydrophobic interactions among dissolved CO 2 molecules. • Cation and anion exhibit different interference patterns in the growth of hydrate. [ABSTRACT FROM AUTHOR]

Grain Boundaries and voids are common defects in nanocrystalline metals, playing pivotal roles in plastic deformation. This study conducted molecular dynamics simulation to explore the incipient plasticity of Σ5 STGB bicrystalline Cu with a spherical void, alongside its constituent monocrystals at 10 K. The results reveal homogeneous nucleation of an elliptical 1/6<112> Shockley partial dislocation loop in the monocrystals. In the void-free Σ5 STGB bicrystal, initial dislocation nucleates homogeneously in grain interior rather than from the Σ5 STGB, forming a Shockley partial dislocation loop. In the monocrystals with a large spherical void, four initial dislocations nucleate from void surface on four slip systems. In the Σ5 STGB bicrystals with a spherical void, when the void diameter is 0.5 nm, the initial dislocation is an arc-shaped Shockley partial dislocation nucleated from the Σ5 STGB. For void diameters larger than 0.5 nm, initial dislocations nucleate from void surface. Through this study, the conditions for the nucleation, number, and morphology of initial dislocations are further understood, facilitating the evaluation of subsequent plastic deformation. This research contributes theoretical underpinnings for improving the mechanical properties and designing high-performance nanocrystalline metals. [Display omitted] • Initial dislocations nucleation begins with local lattice transition. • Nucleation of a Shockley partial dislocation loop in void free single crystal. • Initial dislocation nucleates in grain interior in the void free Σ5 STGB bicrystal. • Dislocation nucleation transits from GB to void surface at D = 0.5 nm. • 4 initial dislocations nucleate from large void surface, while 2 from small void. [ABSTRACT FROM AUTHOR]

[GeTe] m -[Sb 2 Te 3 ] n superlattice (GST-SL) is a promising material candidate to solve the critical problem of high-power consumption for phase-change memory technology. However, the switching mechanism is still under strong debate during the last decade. A key controversial question is that whether melting in GST-SL is possible. In this work, a large-scale machine learning interatomic potential (MLIP) molecular dynamics (MD) simulation with a one-order-of-magnitude larger atom number than that of conventional density functional theory (DFT) MD captures a unique partial melting behavior in GST-SL, where a sparse-nucleation-and-growth governed melting behavior is triggered by the flipping of atoms into van der Waals (vdW) gaps and forming cation-in-vdW-gap (CiV) defect as starting point, and then is slowly developed via propagating liquid-crystalline interfaces. In great contrast, the traditional melting of rock salt (RS)-GST occurs very fast due to instant homogeneous nucleation from high-density intrinsic vacancies distributed randomly in its cubic lattice. Therefore, the melting regions in GST-SL can be spatially localized in form of partial melting and are readily controlled. Moreover, the atomic distribution after melting in GST-SL is more chemical ordering than that in RS-GST. By the large-scale MLIP-MD, the present study provides a critical atomic insight into GST-SL phase-change behaviors that conventional DFT-MDs hardly achieve. This partial-melting nature in GST-SL helps explain the long-term-confused working principle of GST-SL-based phase-change memory, which will accelerate its application in the big-data era. [Display omitted] [ABSTRACT FROM AUTHOR]

Previous work on studying FCC/BCC martensite transformations using molecular dynamics (MD) was mainly adopting an atomistically flat interface between the two transforming phases as initial structural model, whereas recent HRTEM observations show that martensitic interfaces are comprised of atomic terraces with regularly distributed steps reticulated by interfacial defects. In this work, migration behavior of stepped FCC/BCC martensitic interface aided by disconnections is studied using MD simulation method, and two typical orientation relationships (ORs), i.e., Kurdjumov–Sachs (KS) and Nishiyama–Wassermann (NW) ORs, commonly found in ferrous alloys are considered. For both ORs, the stepped interfaces maintain a macroscopically planar morphology as they advance in constant velocities by the collective motion of disconnections in the absence of homogeneous nucleation. The migration velocities of interfaces as obtained are 550 and 90 m·s−1 for the NW and KS ORs, respectively, showing good agreement with published experimental measurements. The disconnections under the NW OR exhibit edge defect character and move laterally along the terrace plane at a velocity approaching the speed of sound, while remaining straight along their dislocation lines, whereas the disconnections under the KS OR possess screw defect character and migrate in a zigzag and sluggish manner through cross-slipping on two nonparallel planes of { 101 } BCC by a kink pair mechanism. By implementing a thin slab of atoms as tracing marker in the simulation model, the transformation shear accompanying the interface motion can be quantified and the so-determined transformation shear angles show good agreement with experimental measurements. The results provide a physical insight into the interrelations between interface structure and transformation process, which is crucial for understanding the atomic mechanism of martensitic transformations. [ABSTRACT FROM AUTHOR]

In this study, we used molecular dynamics (MD) simulations to investigate the atomic ordering in the liquid aluminum (Al) adjacent to the amorphous substrate with smooth and rough surfaces. This study revealed that the liquid exhibited layering within about 5 atomic layers but no visible in-plane atomic ordering at the interface with the smooth amorphous surface, and neither layering nor in-plane atomic ordering with the rough surface of the amorphous substrate. However, the smooth amorphous surface induced some local ordered structure in the liquid at the interface by a structural templating mechanism, which promoted heterogeneous nucleation by creating a 2-dimensional (2D) nucleus in the third layer. The amorphous substrate with a rough surface had no effect on the nucleation in the liquid, leading to the occurrence of homogeneous nucleation with an undercooling 100 K larger than that of heterogeneous nucleation on the smooth amorphous substrate. This study confirmed that structural templating is a general mechanism for heterogeneous nucleation. [ABSTRACT FROM AUTHOR]

Molecular simulations have provided valuable insight into the microscopic mechanisms underlying homogeneous ice nucleation. While empirical models have been used extensively to study this phenomenon, simulations based on first-principles calculations have so far proven prohibitively expensive. Here, we circumvent this difficulty by using an efficient machine-learning model trained on density-functional theory energies and forces. We compute nucleation rates at atmospheric pressure, over a broad range of supercoolings, using the seeding technique and systems of up to hundreds of thousands of atoms simulated with ab initio accuracy. The key quantity provided by the seeding technique is the size of the critical cluster (i.e., a size such that the cluster has equal probabilities of growing or melting at the given supersaturation), which is used together with the equations of classical nucleation theory to compute nucleation rates. We find that nucleation rates for our model at moderate supercoolings are in good agreement with experimental measurements within the error of our calculation. We also study the impact of properties such as the thermodynamic driving force, interfacial free energy, and stacking disorder on the calculated rates. [ABSTRACT FROM AUTHOR]

The kinetics of homogeneous nucleation of the vapour-gas phase was studied by the molecular dynamics (MD) method in Lennard-Jones systems simulating solutions with partial (A) and complete (B) solubility of components. The calculations were carried out at a temperature close to the normal boiling point of the solvent, two concentrations of the solute, and negative pressures. The pressure, as a function of density and concentration, in stable and metastable states, the parameters of phase equilibrium at a flat interface were determined. The ultimate stretching Δpn = ps–pn exceeded than those calculated from the classical nucleation theory at concentrations of solute c > 0.14 and were less theoretical ones at c < 0.2 in solutions A and B, respectively. A qualitative difference in the formation and growth of the vapour-gas nucleus in solutions A and B was established. In solution A, the partial density of the solvent sharply decreases and the density of the volatile component increases at the region of the bubble formation. In solution B, the density of the volatile component inside the bubble remains close to the density in the surrounding phase, and the density of the solvent decreases at the initial stage of bubble formation. [ABSTRACT FROM AUTHOR]

Homogeneous freezing nucleation occurs in supercooled liquid water by the formation of critical-sized ice embryos. Molecular Dynamics simulations were performed 'sowing' a solid embryo into liquid and monitoring the subsequent system evolution. The size of critical ice embryos and the activation energy barrier associated with the incorporation of molecules into the germ were estimated using the TIP5P-E water model for three different temperatures: 237, 240 and 244 K. The results show how MD simulations provide reliable outcomes for the study of both parameters. [ABSTRACT FROM AUTHOR]

It is well known that initial defects play an essential role in the dynamic failure of materials. In practice, dynamic tension is often realized by release of compression waves. In this work, we consider void-included single-crystal aluminum and investigate the damage characteristics under different shock compression and release based on direct atomistic simulations. Elastic deformation, limited growth and closure of voids, and the typical spall and new nucleation of voids were all observed. In the case of elastic deformation, we observed the oscillatory change of void volume under multiple compression and tension. With the increase of impact velocity, the void volume reduced oscillations to the point of disappearance with apparent strain localization and local plastic deformation. The incomplete or complete collapsed void became the priority of damage growth under tension. An increase in sample length promoted the continuous growth of preset void and the occurrence of fracture. Of course, on the release of strong shock, homogeneous nucleation of voids covered the initial void, leading to a wider range of damaged zones. Finally, the effect of the preset void on the spall strength was presented for different shock pressures and strain rates. [ABSTRACT FROM AUTHOR]

Zirconium (Zr) alloys are widely used as structural materials in the core of nuclear reactors. However, the absorption of hydrogen by these alloys during the reactor operation may lead to the precipitation of hydrides. Such hydrides have considerable effects on the microstructure and mechanical properties of the alloys, thus significantly impacting their overall performance. In this work, we investigate the behavior of hydrogen in the presence of symmetric tilt grain boundaries in Zr using molecular dynamics simulations. To systematically explore the conditions for the formation of hydrides, we consider hydrogen concentration levels of up to 50 at.%. We find that hydrogen concentrations of 30 at.% or lower are below the threshold for the precipitation of hydrides, while fcc coordinated hydrides precipitate at 50 at.%, which is very close to the solubility limit of hydrogen in Zr at 800 K. We find that the grain boundaries (GBs) play a pivotal role in the behavior of hydrogen, as well as the formation of hydrides in Zr systems. In most cases, large amounts of hydrogen are found to accumulate at GBs. However, both homogeneous and heterogeneous nucleation are observed during the formation of hydrides at the grain interiors and GBs, respectively. Nonetheless, in some cases the GB inhibit the formation of hydrides. [ABSTRACT FROM AUTHOR]

Co-crystal formation from fluid-mixtures is quite common in a large number of systems. The simplest systems that show co-crystal (also called substitutionally ordered solids) formation are binary hard sphere mixtures. In this work, we study the nucleation of AB2 type solid compounds using Monte Carlo molecular simulations in binary hard sphere mixtures with the size ratio of 0.55. The conditions chosen for the study lie in the region where nucleation of an AB2 type solid competes with that of a pure A solid with a face-centered-cubic structure. The fluid phase composition is kept equal to that of the AB2 type solid. The nucleation free-energy barriers are computed using the seeding technique of Sanz et al. [J. Am. Chem. Soc. 135, 15008 (2013)]. Our simulation results show that the nucleation of the AB2 type solid is favored even under conditions where the pure A solid is more stable. This is primarily due to the similarity in the composition of the fluid phase and the AB2 type solid which in turn leads to much lower interfacial tension between the crystal nucleus and the fluid phase. This system is an example of how the fluid phase composition affects the structure of the nucleating solid phase during crystallization and has relevance to crystal polymorphism during crystallization processes. [ABSTRACT FROM AUTHOR]

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 energieswas 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. [ABSTRACT FROM AUTHOR]

Macroscopic theories of nucleation such as classical nucleation theory envision that clusters of the bulk stable phase form inside the bulk metastable phase. Molecular dynamics simulations are often used to elucidate nucleation mechanisms, by capturing the microscopic configurations of all the atoms. In this paper, we introduce a thermodynamic model that links macroscopic theories and atomicscale simulations and thus provide a simple and elegant framework for testing the limits of classical nucleation theory. [ABSTRACT FROM AUTHOR]

Molecular dynamics (MD) simulations explored the deformation behavior of copper single crystal under various axisymmetric loading paths. The obtained MD dataset was used for the development of a machine-learning-based model of elastic–plastic deformation of copper. Artificial neural networks (ANNs) approximated the elastic stress–strain relation in the form of tensor equation of state, as well as the thresholds of homogeneous nucleation of dislocations, phase transition and the beginning of spall fracture. The plastic part of the MD curves was used to calibrate the dislocation plasticity model by means of the probabilistic Bayesian algorithm. The developed constitutive model of elastic–plastic behavior can be applied to simulate the shock waves in thin copper samples under dynamic impact. [ABSTRACT FROM AUTHOR]

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 9. 6 0 × 1 0 3 3 m − 3 s − 1 . The nucleation rate obtained by the survival probability (SP) is 9. 8 8 × 1 0 3 3 m − 3 s − 1 , 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. The critical crystal nucleus size and nucleation rate of Al at 640 K were obtained by mean first-passage time. According to the Johnson–Mehl–Avrami law, the growth rate of different morphologies is obtained. Among them, LAM grows faster than FFT. During the growth process, the crystal nuclei are ellipsoids of different shapes rather than perfect spheres. [ABSTRACT FROM AUTHOR]

The construction of metallic glasses (MGs) at the atomic scale for molecular dynamics simulations involves several factors that ultimately affect the deformation behaviour, a matter that has been rarely addressed in the literature. In order to explore this issue, 10 Cu 50 Zr 50 MGs with different random initial arrangements were subjected to compression tests under identical simulation conditions. Three different deformation behaviours were identified: weak shear band (SB) formation + homogeneous nucleation of shear transformation zones (STZs); SB formation + weak STZs nucleation; and heavily localised SB formation. Structural characterisation revealed that samples exhibiting localised SB formation presented larger populations of clusters with a high degree of local five-fold symmetry, fivefold and quasi-fivefold bonding. The deformation behaviour also varied from sample to sample when exploring other parameters such as the initial random velocities and the annealing temperature after replication of the small samples. Therefore, the preparation procedure must be considered cautiously when studying MGs ductility. [ABSTRACT FROM AUTHOR]

The classical nucleation theory for homogeneous nucleation is formulated as a theory for a density fluctuation in a supersaturated gas at a given temperature. But molecular dynamics simulations reveal that it is small cold clusters which initiates the nucleation. The temperature in the nucleating clusters fluctuates, but the mean temperature remains below the temperature in the supersaturated gas until they reach the critical nucleation size. The critical nuclei have, however, a temperature equal to the supersaturated gas. The kinetics of homogeneous nucleation is not only caused by a grow or shrink by accretion or evaporation of monomers only but also by an exponentially declining change in cluster size per time step equal to the cluster distribution in the supersaturated gas. [ABSTRACT FROM AUTHOR]

The homogeneous nucleation of crystals of the ionic liquid [dmim+][Cl-] from its supercooled liquid phase in the bulk (P = 1 bar, T = 340 K, representing a supercooling of 58 K) was studied using molecular simulations. The string method in collective variables [Maragliano et al., J. Chem. Phys. 125, 024106 (2006)] was used in combination with Markovian milestoning with Voronoi tessellations [Maragliano et al., J. Chem. Theory Comput. 5, 2589-2594 (2009)] and order parameters for molecular crystals [E. E. Santiso and B. L. Trout, J. Chem. Phys. 134, 064109 (2011)] to sketch a minimum free energy path connecting the supercooled liquid and the monoclinic crystal phases, and to determine the free energy and the rates involved in the homogeneous nucleation process. The physical significance of the configurations found along this minimum free energy path is discussed with the help of calculations based on classical nucleation theory and with additional simulation results obtained for a larger system. Our results indicate that, at a supercooling of 58 K, the liquid has to overcome a free energy barrier of the order of 60 kcal/mol and to form a critical nucleus with an average size of about 3.6 nm, before it reaches the thermodynamically stable crystal phase. A simulated homogeneous nucleation rate of 5.0 × 1010 cm-3 s-1 was obtained for our system, which is in reasonable agreement with experimental and simulation rates for homogeneous nucleation of ice at similar degrees of supercooling. This study represents our first step in a series of studies aimed at understanding the nucleation and growth of crystals of organic salts near surfaces and inside nanopores. [ABSTRACT FROM AUTHOR]

We perform direct large molecular dynamics simulations of homogeneous SPC/E water nucleation, using up to ~4 · 106 molecules. Our large system sizes allow us to measure extremely low and accurate nucleation rates, down to ~1019 cm-3 s-1, helping close the gap between experimentally measured rates ~1017 cm-3 s-1. We are also able to precisely measure size distributions, sticking efficiencies, cluster temperatures, and cluster internal densities. We introduce a new functional form to implement the Yasuoka-Matsumoto nucleation rate measurement technique (threshold method). Comparison to nucleation models shows that classical nucleation theory over-estimates nucleation rates by a few orders of magnitude. The semi-phenomenological nucleation model does better, under-predicting rates by at worst a factor of 24. Unlike what has been observed in Lennard-Jones simulations, post-critical clusters have temperatures consistent with the run average temperature. Also, we observe that post-critical clusters have densities very slightly higher, ~5%, than bulk liquid. We re-calibrate a Hale-type J vs. S scaling relation using both experimental and simulation data, finding remarkable consistency in over 30 orders of magnitude in the nucleation rate range and 180 K in the temperature range. [ABSTRACT FROM AUTHOR]

In this paper, based on the embedded atom method (EAM) potential, molecular dynamics simulations of the solidification process of Al–4 at.%Cu alloy is carried out. The Al–Cu alloy melt is placed at different temperatures for isothermal solidification, and each stage of the entire solidification process is tracked, including homogeneous nucleation, nucleus growth, grain coarsening and microstructure evolution. In the nucleation stage, the transition from high temperature to low temperature manifests a change from spontaneous nucleation mode to divergent nucleation mode. The critical nucleation temperature of the Al–Cu alloy is determined to be about 0.42 Tm (Tm is the melting point of Al–4 at.%Cu) by calculating the nucleation rate and the crystal nucleus density. In the nucleus growth stage, two ways of growing up are observed, that is, a large crystal nucleus will absorb a smaller heterogeneous crystal nucleus, and two very close crystal nuclei will merge. In the microstructure evolution of the isothermally solidified Al–Cu alloy, it is emerged that the interior of all nanocrystalline grains are long-period stacking structure composed of face centred cubic (FCC) and hexagonal close-packed (HCP). These details provide important information for the production of Al–Cu binary alloy nano-polycrystalline products.

Transparent glass ceramics (TGCs) have shown great prospects in many application fields. Understanding the effect of oxides on glass network structure and crystallization is essential for designing TGCs. A series of 18Na 2 O-(16-x)CaO-xMgO-3P 2 O 5 -2.5Al 2 O 3 -60.5SiO 2 (mol%, x = 0, 4, 8, 12, 16) glass-ceramics were studied with Molecular dynamics (MD) simulations, and the effect of CaO substituted by MgO on the glass structure and crystallization was analyzed in details. The results show that MgO statistically behaves as a network former, and the overall network connectivity increases with the substitution of MgO for CaO. Further structure analysis shows that the complex glass system consists of Si-rich and P-rich phases, which respectively contain Si-Mg-rich regions with 2Mg1Si-related tricluster oxygens (TBOs) and P-Mg-rich regions. The energetically unfavorable TBOs and Mg 4 -O-Mg 4 linkages provide favorable nucleation sites for homogeneous nucleation, and the so-called 'Coordination matching' principles are proposed to explain the type of crystals. These results help us understand the crystallization of Mg-containing glass ceramics and benefit the future design of novel spontaneous TGCs. [ABSTRACT FROM AUTHOR]

In this work, we evaluate by means of computer simulations the rate for ice homogeneous nucleation for several water models such as TIP4P, TIP4P/2005,TIP4P/ICE, and mW (following the same procedure as in Sanz et al. [J. Am. Chem. Soc.135, 15008 (2013)]) in a broad temperature range. We estimate the ice-liquid interfacial free-energy, and conclude that for all water models γ decreases as the temperature decreases. Extrapolating our results to the melting temperature, we obtain a value of the interfacial free-energy between 25 and 32 mN/m in reasonable agreement with the reported experimental values. Moreover, we observe that the values of γ depend on the chosen water model and this is a key factor when numerically evaluating nucleation rates, given that the kinetic prefactor is quite similar for all water models with the exception of the mW (due to the absence of hydrogens). Somewhat surprisingly the estimates of the nucleation rates found in this work for TIP4P/2005 are slightly higher than those of the mW model, even though the former has explicit hydrogens. Our results suggest that it may be possible to observe in computer simulations spontaneous crystallization of TIP4P/2005 at about 60 K below the melting point. [ABSTRACT FROM AUTHOR]

• Thermophysical properties and condensation process of R1233zd(E) were simulated. • Phase transition rate of R1233zd(E) increase as p sim increases or t sim decreases. • E vdw gives greatest contribution to e p change during phase change process. • R1233zd(E) has faster condensation rate than R1234ze(E), R1243zf and R1234yf. R1233zd(E) is one promising alternative refrigerant with excellent environmental-friendly performance. In this paper, the molecular dynamics simulation method was used to study the density, heat capacity and homogeneous condensation nucleation process of R1233zd(E) from a superheated state to different supercooled states aiming to provide information for its application. The higher condensation pressure and lower condensation temperature was found to be favorable to increase condensation rate of R1233zd(E). During the nucleation process, the molecular distribution of R1233zd(E) becomes uneven; meanwhile, the potential energy has a sharp drop which is mostly caused by the drop of van der Waals energy. The faster condensation rate of R1233zd(E) compared to other three HFOs R1234ze(E), R1243zf and R1234yf is helpful to improve refrigeration efficiency. [ABSTRACT FROM AUTHOR]

Dynamic tensile (spall) fracture of pure Pb and Sn in solid and molten states is investigated by MD simulations. The influence of unwettable inclusions on the spall strength is revealed. Mechanical model of fracture is fitted to MD data at the strain rate 10 9 s - 1 and used for calculation of the rate dependencies of spall strength in the range from 10 4 s - 1 to 10 9 s - 1 in comparison with the experimental data. The model takes into account homogeneous nucleation of pores, activation of pores on unwettable inclusions or other heterogeneities and change in pore size, which is viscous for melt and elastic-plastic for solid. In the case of pure uniform material, the homogeneous nucleation gives a slow decrease in spall strength with decreasing strain rate; the calculated values significantly exceed experimental results for moderate strain rates of 10 4 – 10 5 s - 1 . Accounting of unwettable inclusions removes this contradiction and provides correspondence to experimental data. A power-law size distribution of inclusions gives in the case of melt the power-law dependence of spall strength on strain rate that coincides with the experimental data for molten Sn. In the case of solid metal, the spall strength at moderate strain rates is determined by the yield strength. Therefore, the initial power law decrease in the spall strength is replaced by almost constant level at moderate strain rates. This behavior corresponds to the existing experimental data for solid Pb. Transfer to the homogeneous nucleation mode takes place for solid and molten metals at ultra-high strain rates, when the concentration of pores activated on the existing heterogeneities is not enough for the stress relaxation. [ABSTRACT FROM AUTHOR]

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. Using radial distribution function (RDF), bond distance calculation, angle measurement, and configurational snapshots, it was found that the newly emerged phase is face-centered cubic crystals with some water molecules trapped inside the crystal lattice. It was also shown that during early stages of nucleation, high local density of ions occurred, and within these areas, the nucleation started with a sequence of ionic additions, as suggested by classical nucleation theory. It was concluded that crystal nuclei form in a sequential manner, but this can only happen in places where the local density of ions (supersaturation) is higher than the solution concentration, and the probability of having effective collisions increases, making these sites primary candidates for nucleation. [ABSTRACT FROM AUTHOR]

• The melting and homogeneous nucleation of Na crystals were studied by MD simulation. • The rationality of the EAM/FS potential model has been verified. • Na's Q and T m k calculated were 1.6406·10−20J and 468.3 K, respectively. • The ln D and ln (I hom) of Na crystal melting vs temperature were given, respectively. • The I hom of Na crystal melting increases exponentially with rising temperature. 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 (I hom), 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 I hom 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 I hom 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. [ABSTRACT FROM AUTHOR]

Nanoindentation has been used for a long time to investigate the mechanical properties of materials. A well-known displacement burst, the so-called "pop-in," is usually observed during nanoindentation tests. In particular for the first pop-in has been well studied because it should be directly related to the fundamental mechanical strength of the local volume beneath the indenter. The first pop-in load measured for a defect-free local volume is corresponding to the onset load of homogeneous dislocation nucleation, while measured for a local volume with immobile defects is that of heterogeneous dislocation nucleation. The first pop-in is a thermally activated event under loading; thus, the pop-in load exhibits both temperature and loading-rate dependencies. Although theoretical studies have successfully explained the temperature and loading-rate dependencies, to the best of our knowledge, an atomistic prediction for specific materials which takes into account the stress state beneath the indenter has not yet been reported. In this study, we propose an atomistically informed multiscale (two-scale) modeling to predict the temperature and loading-rate dependencies of the first pop-in load for the homogeneous dislocation nucleation considering an atomistically estimated stress state beneath the indenter and stress-dependent activation energies of dislocation nucleation. Body-centered-cubic Fe and Ta are chosen as target metals, although the method is generally applicable to any ductile material. In addition to the homogeneous dislocation nucleation, we also developed a heterogeneous nucleation theory to explain the difference between the experimentally and atomistically obtained homogeneous nucleation pop-in loads. • Modeling for predicting temperature/loading-rate dependencies of first pop-in load. • Atomistic modeling in the case of homogeneous dislocation nucleation is proposed. • The model can fully take into account actual stress distribution beneath indenter. • Rate-based heterogeneous dislocation nucleation model is also developed. • It can explain the broadness of experimental first pop-in cumulative probability. [ABSTRACT FROM AUTHOR]

Methane hydrates have important industrial and climate implications, yet their formation via homogeneous nucleation under natural, moderate conditions is poorly understood. Obtaining such understanding could lead to improved control of crystallization, as well as insight into polymorph selection in general, but is hampered by limited experimental resolution. Direct molecular dynamics simulations using atomistic force fields could provide such insight, but are not feasible for moderate undercooling, due to the rare event nature of nucleation. Instead, we harvest ensembles of the rare unbiased nucleation trajectories by employing transition path sampling.We find that with decreasing undercooling the mechanism shifts from amorphous to crystalline polymorph formation. At intermediate temperature the 2 mechanisms compete. Reaction coordinate analysis reveals the amount of a specific methane cage type is crucial for crystallization, while irrelevant for amorphous solids. Polymorph selection is thus governed by kinetic accessibility of the correct cage type and, moreover, occurs at precritical nucleus sizes, apparently against Ostwald's step rule. We argue that these results are still in line with classical nucleation theory. Our findings illuminate how selection between competing methane hydrate polymorphs occurs and might generalize to other hydrates and molecular crystal formation. [ABSTRACT FROM AUTHOR]

Abstract 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. Highlights • Nucleation of liquid drops in a superheated Lennard-Jones crystal is investigated. • The method of molecular dynamics (MD) simulation is used. • A considerable discrepancy between data of MD simulation and CNT has been established. • It is shown that discrepancy is connected with the work of critical nucleus formation. [ABSTRACT FROM AUTHOR]

• Atomistic simulations were conducted to study the decay of a superheated AlCu alloy. • The AlCu model was constructed using an artificial neural network machine-learning approach. • The Classical Nucleation Theory accurately described the melting of the AlCu alloy, without any adjustable parameters. The validity of the Classical Nucleation Theory (CNT), the standard tool for describing and predicting nucleation kinetics in metastable systems, has been under scrutiny for almost a century. While the CNT is commonly employed to describe liquid → crystal and liquid ↔ vapor phase transitions, its application to the crystal → liquid case has been limited because of the experimental challenges in achieving superheating states and detecting homogeneous liquid nucleation. In this study, we performed comprehensive molecular dynamics (MD) simulations of spontaneous melting of a superheated AlCu crystal under atmospheric pressure at five temperatures, covering a superheating range of T / T L = 1.1–1.3, where T L is the liquidus temperature. Two realistic AlCu models were investigated: one described by the modified embedded atom method (MEAM) and the other by an interatomic potential generated by an artificial neural network machine learning (ML) approach, extensively trained on an ab initio dataset of liquid and crystal configurations. Fifty independent melting events were simulated at each temperature. By analyzing the distribution of melting times using the Poisson law, the homogeneous nucleation rate was determined through the mean lifetime method. Additionally, the Zeldovich factor, critical nucleus size, and work of formation were obtained using the mean first-passage time method, utilizing the disorder parameter based on atomic displacements (liquid-like atoms in the superheated crystal) as the reaction coordinate. Also, the effective atomic transport coefficient across the metastable crystal/critical liquid nucleus interface was determined by MD simulations as the interfacial attachment coefficient for nuclei growth rates. Using these simulation-generated data, the theoretical nucleation rates were calculated by the CNT with no fitting parameters. We found excellent agreement between the theoretically and MD-computed liquid nucleation rates for both MEAM and ML crystals. Notably, the effective solid-liquid interfacial free energy value obtained from the MD data aligns with its recent experimental measure. Moreover, the CNT qualitatively and quantitatively described the underlying details of liquid drop nucleation in our ML solid, unprecedentedly and accurately reproducing the kinetic prefactor and the size, formation energy, and growth rate of the critical nuclei. Thus, the melting of the AlCu model created through machine learning-processed quantum calculations, that is, not relying on hand-crafted interatomic potential functions, was successfully described by the CNT phenomenological formalism, without any adjustable parameters. This finding confirms the CNT as a very reliable descriptor of homogeneous nucleation in the superheated AlCu alloy and generalizes this theory as a powerful tool for analyzing and predicting the kinetics of crystal-liquid transitions. [ABSTRACT FROM AUTHOR]

• Shock response of single and nanocrystalline CoCrFeMnNi HEAs are studied. • The shock wave and the reversibility of deformation are anisotropic. • SRO slightly increases the spall strength but reduces the ductility. • SRO and grain boundary influence the chemical heterogeneity in shocked HEA. • The effects of individual element effects in CoCrFeMnNi HEA are revealed. Shock-induced deformation and fracture in single-crystalline and nanocrystalline CoCrFeMnNi high-entropy alloys (HEAs) under different shock intensities are investigated systematically using large-scale molecular dynamics simulations. The strong anisotropy in the single-crystalline HEA and how the reversibility of HCP-structured atoms influences the void nucleation and growth are revealed. Specifically, shock-induced FCC to HCP structural transformations are largely reversible in the case of the [001] loading direction, leading to homogeneous void nucleation; while they are largely irreversible in the cases of the [110] and [111] loading directions, resulting in void nucleation in the intersection of HCP layers. In nanocrystalline HEA, the deformations in the grain interior are similar to those in the single crystals, while the grain boundaries serve as void nucleation sites and thus weaken the spall strength. The SRO effects on the shock response in single-crystalline and nanocrystalline CoCrFeMnNi HEA are revealed, and the chemical heterogeneity is analyzed. Our results show that SRO can only slightly increase the shear stress and the spall strength, but it can cause a reduction of ductility during the spallation. The differences in SRO effects between single-crystalline and nanocrystalline models are attributed to the grain boundaries, where Cr and Mn are favorable, while Ni is favored inside the grains in the SRO model. Moreover, the comparison between CoCrFeMnNi HEA and its subsystem as well as single-element metal indicates Mn seems to be the most influential elements in CoCrFeMnNi HEA, resulting in significant changes in strength. A relation between the spall strength and strain rate is proposed to describe the simulation results and reported experimental data. Our comprehensive and systematical studies provide deep insights into the deformation and fracture in CoCrFeMnNi HEA subjected to shock loading, which deepens the understanding on the dynamic deformations of CoCrFeMnNi HEA and benefits the rational design of new HEAs/MEAs with enhanced performance. [Display omitted] [ABSTRACT FROM AUTHOR]