One of most intriguing problems of heterogeneous crystal nucleation in droplets is its strong enhancement in the contact mode (when the foreign particle is presumably in some kind of contact with the droplet surface) compared to the immersion mode (particle immersed in the droplet). Many heterogeneous centers have different nucleation thresholds when they act in contact or immersion modes, indicating that the mechanisms may be actually different for the different modes. Underlying physical reasons for this enhancement have remained largely unclear. In this paper we present a model for the thermodynamic enhancement of heterogeneous crystal nucleation in the contact mode compared to the immersion one. To determine if and how the surface of a liquid droplet can thermodynamically stimulate its heterogeneous crystallization, we examine crystal nucleation in the immersion and contact modes by deriving and comparing with each other the reversible works of formation of crystal nuclei in these cases. As a numerical illustration, the proposed model is applied to the heterogeneous nucleation of Ih crystals on generic macroscopic foreign particles in water droplets at T=253 K. Our results show that the droplet surface does thermodynamically favor the contact mode over the immersion one. Surprisingly, our numerical evaluations suggest that the line tension contribution to this enhancement from the contact of three water phases (vapor-liquid-crystal) may be of the same order of magnitude as or even larger than the surface tension contribution.
Phase transformations such as freezing typically start with heterogeneous nucleation. Heterogeneous nucleation near a wetting transition, of a crystalline phase is studied. The wetting transition occurs at or near a vapour-liquid transition which occurs in a metastable fluid. The fluid is metastable with respect to crystallisation, and it is the crystallisation of this fluid phase that we are interested in. At a wetting transition a thick layer of a liquid phase forms at a surface in contact with the vapour phase. The crystalline nucleus is then immersed in this liquid layer, which reduces the…
By focusing a high intensity acoustic wave in liquid helium, we have observed the nucleation of solid helium inside the wave above a certain threshold in amplitude. The nucleation is a stochastic phenomenon. Its probability increases continuously from 0 to 1 in a narrow pressure interval around Pm + 4.7 bars (Pm is the melting pressure where liquid and solid helium are in equilibrium). This overpressure is larger by two to three orders of magnitude than what had been previously observed. Our result strongly supports a recent suggestion by Balibar, Mizusaki and Sasaki that, in all previous expe…
We investigate heterogeneous and homogeneous nucleation in nearest-neighbor and long-range Ising models for various quench depths. We find that the system has a true crossover from heterogeneous to homogeneous nucleation for increasing quench depth only if the interaction is sufficiently long-range. The survival curves, defined as the fraction of systems that remain in the metastable state after a given time, have qualitatively different shapes as a function of quench depth for heterogeneous and homogeneous nucleation when the interaction is short-range, but have identical shapes within the ac…
In the standard treatment of heterogeneous nucleation on a surface, the energy of the surface is assumed to be homogeneous. Often its value is obtained from some macroscopic measurement. We ask the question what happens if we consider the surface energy to be heterogeneous. This is a straightforward generalization and may realistically be important in a number of scenarios, e.g. when the phase forming the surface is a binary alloy, solid solution, in presence of self-organized or artifically created patterns on the surface. We examine the effects of surface heterogeneity in a few scenarios in …
We consider the problem of heterogeneous nucleation and growth. The system is described by a phase field model in which the temperature is included through thermal noise. We show that this phase field approach is suitable to describe homogeneous as well as heterogeneous nucleation starting from several general hypotheses. Thus we can investigate the influence of grain boundaries, localized impurities, or any general kind of imperfections in a systematic way. We also put forward the applicability of our model to study other physical situations such as island formation, amorphous crystallization…
Vapor condensation on nanoparticle with radius smaller than the Kelvin radius is considered as fluctuation or as the heterogeneous nucleation. The expression for steady-state heterogeneous nucleation rate is obtained. Nucleation on negatively charged nanoparticles is discussed. The report was made at 17th International Nucleation and Atmospheric Conferences, Galway, Ireland, 2007.
In simulations of the 2D Ising model, we examine heterogeneous nucleation induced by a small impurity consisting of a line of $l$ fixed spins. As $l$ increases, we identify a limit of stability beyond which the metastable phase is not defined. We evaluate the free energy barrier for nucleation of the stable phase, and show that contrary to expectation, the barrier does not vanish on approach to the limit of stability. We also demonstrate that our values for the height of the barrier yield predictions for the nucleation time (from transition state theory) and the size of the critical cluster (f…
We develop a stochastic approach for describing 3D-phase transformations ruled by time-dependent correlated nucleation at solid surfaces. The kinetics is expressed as a series of correlation functions and, at odds with modeling based on Poisson statistics, it is formulated in terms of actual nucleation rate. It is shown that truncation of the series up to second order terms in correlation functions provides a very good approximation of the kinetics. The time evolution of both total amount of growing phase and surface coverage by the new phase have been determined. The theory is applied to desc…
The homogeneous and heterogeneous nucleation of a Lennard-Jones liquid is investigated using the umbrella sampling method. The free energy cost of forming a nucleating droplet is determined as a function of the quench depth, and the saddle point nature of the droplets is verified using an intervention technique. The structure and symmetry of the nucleating droplets is found for a range of temperatures. We find that for deep quenches the nucleating droplets become more anisotropic and diffuse with no well defined core or surface. The environment of the nucleating droplets form randomly stacked …
Flat walls facilitate the condensation of a supersaturated vapor: Classical theory of heterogeneous nucleation predicts that the free energy barrier $ΔF_{\rm het}^*$ which needs to be overcome for the formation of sphere-cap shaped nucleation seeds is smaller than the barrier $ΔF^*_{\rm hom}$ for spherical droplets in the bulk by a factor $0<f(θ)<1$, which only depends on the contact angle $θ$. In this letter we compute both $ΔF^*_{\rm hom}$ and $ΔF^*_{\rm het}$ from Monte Carlo simulations and test the theory for the lattice gas model (for which $θ$ can be readily controlled). Even though the…
We study the heterogeneous nucleation of Ising model on complex networks under a non-equilibrium situation where the impurities perform degree-biased motion controlled by a parameter α. Through the forward flux sampling and detailed analysis on the nucleating clusters, we find that the nucleation rate shows a nonmonotonic dependence on αfor small number of impurities, in which a maximal nucleation rate occurs at α=0 corresponding to the degree-uncorrelated random motion. Furthermore, we demonstrate the distinct features of the nucleating clusters along the pathway for different preference of i…
Despite its importance in atmospheric science, much remains unknown about the microscopic mechanism of heterogeneous ice nucleation. In this work, we perform hybrid Monte Carlo simulations of the heterogeneous nucleation of ice on a range of generic surfaces, both flat and structured, in order to probe the underlying factors affecting the nucleation process. The structured surfaces we study comprise one basal plane bilayer of ice with varying lattice parameters and interaction strengths. We show that what determines the propensity for nucleation is not just the surface attraction, but also the…
A phase eld approach is developed to model wetting and heterogeneous crystal nucleation of an undercooled pure liquid in contact with a sharp wall. We discuss various choices for the boundary condition at the wall and determine the properties of critical nuclei, including their free energy of formation and the contact angle as a function of undercooling. We nd for particular choices of boundary conditions, we may realize either an analog of the classical spherical cap model or decidedly non-classical behavior, where the contact angle decreases from its value taken at the melting point towards …
Glass-like arrest of kinetics has been observed across many magnetic first-order transitions. By traversing the two control variable H-T space, tunable coexisting fractions of arrested and equilibrium phases have been observed. We report here a fortuitous situation in a half-doped manganite sample, where these features occur by varying only temperature (T) along the H=0 line. The resistivity at 5 K rises by more than a factor of three provided second cool-down is effected from a specified intermediate T. This significant enhancement results from heterogeneous nucleation during second cool-down…
In principle, the answer to the posed titular question is undoubtedly 'yes.' But in practice, requisite reference data for homogeneous systems have been obtained with a treatment of intermolecular interactions that is different from that typically employed for heterogeneous systems. In this article, we assess the impact of the choice of truncation scheme when comparing water in homogeneous and inhomogeneous environments. Specifically, we use explicit free energy calculations and a simple mean field analysis to demonstrate that using the 'cut-and-shift' version of the Lennard-Jones potential (c…
Computational studies of crystal nucleation can be impacted by finite size effects, primarily due to unphysical interactions between crystalline nuclei and their periodic images. It is, however, not always feasible to systematically investigate the sensitivity of nucleation kinetics and mechanism to system size due to large computational costs of nucleation studies. Here, we use jumpy forward flux sampling to accurately compute the rates of heterogeneous ice nucleation in the vicinity of square-shaped model structureless ice nucleating particles (INPs) of different sizes, and identify three di…
We have investigated the temperature driven first order metal-insulator (M-I) transition in thin films of NdNiO$_3$ and have compared it with the bulk behavior. The M-I transition of thin films is sensitive to epitaxial strain and a partial relaxation of epitaxial strain creates an inhomogeneous strain field in the films which broadens the M-I transition. Both the thin film and the bulk samples exhibit non equilibrium features in the transition regime which are attributed to the presence of high temperature metallic phases in their supercooled state. The degree of supercooling in the thin film…
Identifying nucleation pathway is important for understanding the kinetics of first-order phase transitions in natural systems. In the present work, we study nucleation pathway of the Ising model in homogeneous and heterogeneous networks using the forward flux sampling method, and find that the nucleation processes represent distinct features along pathways for different network topologies. For homogeneous networks, there always exists a dominant nucleating cluster to which relatively small clusters are attached gradually to form the critical nucleus. For heterogeneous ones, many small isolate…
We probe through magnetization and resistivity measurements a kinetically arrested glass-like but long-range ordered magnetic state. The transformation kinetics of the magnetic field-temperature induced broad first-order transition from ferromagnetic-metallic (FMM) to antiferromagnetic-insulating (AFI) state gets hindered at low temperature in a La(0.5)Ca(0.5)MnO3 sample. A fraction of high-temperature FMM phase persists to the lowest temperature, albeit as a non-ergodic state. We present a phenomenology for this glass-like but long-range order FMM phase which devitrifies on heating and conver…
We present a computer simulation study on crystal nucleation and growth in supersaturated suspensions of mono-disperse hard spheres induced by a triangular lattice substrate. The main result is that compressed substrates are wet by the crystalline phase (the crystalline phase directly appears without any induction time), while for stretched substrates we observe heterogeneous nucleation. The shapes of the nucleated crystallites fluctuate strongly. In the case of homogeneous nucleation amorphous precursors have been observed (Phys. Rev. Lett. {\bf 105}(2):025701 (2010)). For heterogeneous nucle…
The theoretical description of the heterogeneous nucleation kinetics is presented. This description takes into account the perturbation of the vapor phase initiated by the growing droplets. The form of the density profile around the growing droplet is analyzed which leads to some special approximations. Then the process of nucleation in the whole system is described. As the result all main characteristics of the process are determined analytically.
It is surprisingly difficult to freeze water. Almost all ice that forms under "mild" conditions (temperatures > -40 degrees Celsius) requires the presence of a nucleating agent - a solid particle that facilitates the freezing process - such as clay mineral dust, soot or bacteria. In a computer simulation, the presence of such ice nucleating agents does not necessarily alleviate the difficulties associated with forming ice on accessible timescales. Nevertheless, in this work we present results from molecular dynamics simulations in which we systematically compare homogeneous and heterogeneous i…
The heterogeneous condensation of a Lennard-Jones vapor onto a nanoscale seed particle is studied using molecular dynamics simulations. Measuring the nucleation rate and the height of the free energy barrier using the mean first passage time method shows that the presence of a weakly interacting seed has little effect on the work of forming very small cluster embryos but accelerates the rate by lowering the barrier for larger clusters. We suggest that this results from a competition between the energetic and entropic features of cluster formation in the bulk and at the heterogeneity. As the in…
Contact freezing is a mode of atmospheric ice nucleation in which a collision between a dry ice nucleating particle (INP) and a water droplet results in considerably faster heterogeneous nucleation. The molecular mechanism of such enhancement is, however, still a mystery. While earlier studies had attributed it to collision-induced transient perturbations, recent experiments point to the pivotal role of nanoscale proximity of the INP and the free interface. By simulating heterogeneous nucleation of ice within INP-supported nanofilms of two model water-like tetrahedral liquids, we demonstrate t…
Heterogeneous nucleation is studied by Monte Carlo simulations and phenomenological theory, using the two-dimensional lattice gas model with suitable boundary fields. A chemical inhomogeneity of length b at one boundary favors the liquid phase, while elsewhere the vapor is favored. Switching on the bulk field favoring the liquid, nucleation and growth of the liquid phase starting from the region of the chemical inhomogeneity is analyzed. Three regimes occur: for small fields, the critical droplet radius is so large that a critical droplet having the contact angle required by Young's equation i…
Finite size artifacts arise in molecular simulations of nucleation when critical nuclei are too close to their periodic images. A rigorous determination of what constitutes too close is, however, a major challenge. Recently, we devised rigorous heuristics for detecting such artifacts based on our investigation of how system size impacts the rate of heterogeneous ice nucleation (Hussain, Haji-Akbari, \emph{J. Chem. Phys.} \textbf{154}, 014108, \textbf{2021}). We identified the prevalence of critical nuclei spanning across the periodic boundary, and the thermodynamic and structural properties of…
We review how phase-field models contributed to the understanding of various aspects of crystal nucleation including homogeneous and heterogeneous processes, and their role in microstructure evolution. We recall results obtained both by the conventional phase-field approaches that rely on spatially averaged (coarse grained) order parameters in capturing freezing, and by the recently developed phase-field crystal models that work on the molecular scale, while employing time averaged particle densities, and are regarded as simple dynamical density functional theories of classical particles. Besi…
We use the Dynamic Density-Functional Formalism and the Fundamental Measure Theory as applied to a fluid of parallel hard squares to study the dynamics of heterogeneous growth of non-uniform phases with columnar and crystalline symmetries. The hard squares are (i) confined between soft repulsive walls with square symmetry, or (ii) exposed to external potentials that mimic the presence of obstacles with circular, square, rectangular or triangular symmetries. For the first case the final equilibrium profile of a well commensurated cavity consists of a crystal phase with highly localized particle…
The conventional theory of homogeneous and heterogeneous nucleation in a supersaturated vapor is tested by Monte Carlo simulations of the lattice gas (Ising) model with nearest-neighbor attractive interactions on the simple cubic lattice. The theory considers the nucleation process as a slow (quasi-static) cluster (droplet) growth over a free energy barrier $ΔF^*$, constructed in terms of a balance of surface and bulk term of a "critical droplet" of radius $R^*$, implying that the rates of droplet growth and shrinking essentially balance each other for droplet radius $R=R^*$. For heterogeneous…
We show that models for homogeneous and heterogeneous nucleation of D-dimensional droplets in a d-dimensional medium are described in mean-field by a modified Smoluchowski equation for the distribution N(s,t) of droplets masses s, with additional terms accounting for exogenous growth from vapor absorption, and injection of small droplets when the model allows renucleation. The corresponding collision kernel is derived in both cases. For a generic collision kernel K, the equation describes a clustering process with clusters of mass s growing between collision with ds/dt=As^β$, and injection of …
In this work a phenomenological stochastic differential equation is proposed to model the time evolution of the radius of a pre-critical molecular cluster during nucleation (the classical order parameter). Such a stochastic differential equation constitutes the basis for the calculation of the (nucleation) induction time under Kramers' theory of thermally activated escape processes. Considering the nucleation stage as a Poisson rare-event, analytical expressions for the induction time statistics are deduced for both steady and unsteady conditions, the latter assuming the semiadiabatic limit. T…
We propose an approximation for the total ice nucleation rate J=J(T,R) in supercooled water droplets as a function of both droplet radius R and temperature T, taking account of both volume-based and surface-stimulated nucleation modes. Its crucial idea is that, even in the surface-stimulated mode crystal nuclei initially emerge (as sub-critical clusters) homogeneously in the sub-surface layer, not "pseudo-heterogeneously" at the surface. This mode is negligible in large droplets, but becomes increasingly important with decreasing droplet size and is dominant in small droplets. The crossover dr…
A kinetic theory of homogeneous crystal nucleation in unary droplets is presented taking into account that a crystal nucleus can form not only in the volume-based mode (with all its facets within the droplet) but also in the surface-stimulated one (with one of its facets at the droplet surface). The previously developed thermodynamics of surface-stimulated crystal nucleation rigorously showed that if at least one of the facets of the crystal is only partially wettable by its melt, then it is thermodynamically more favorable for the nucleus to form with that facet at the droplet surface rather …
