We introduce a new Forward-Flux Sampling in Time (FFST) algorithm to efficiently measure transition times in rare-event processes in non-equilibrium systems, and apply it to study the first-order (discontinuous) kinetic transition in the Ziff-Gulari-Barshad model of catalytic surface reaction. The average time for the transition to take place, as well as both the spinodal and transition points, are clearly found by this method.
Many turbulent flows undergo drastic and abrupt configuration changes with huge impacts. As a paradigmatic example we study the multistability of jet dynamics in a barotropic beta plane model of atmosphere dynamics. It is considered as the Ising model for Jupiter troposphere dynamics. Using the adaptive multilevel splitting, a rare event algorithm, we are able to get a very large statistics of transition paths, the extremely rare transitions from one state of the system to another. This new approach opens the way for addressing a set of questions that are out of reach through direct numerical …
Nucleation is considered near the pseudospinodal in a one-dimensional $ϕ^4$ model with a non-conserved order parameter and long-range interactions. For a sufficiently large system or a system with slow relaxation to metastable equilibrium, there is a non-negligible probability of nucleation occurring before reaching metastable equilibrium. This process is referred to as transient nucleation. The critical droplet is defined to be the configuration of maximum likelihood that is dynamically balanced between the metastable and stable wells. Time-dependent droplet profiles and nucleation rates are …
We present precision Monte Carlo data and analytic arguments for an asymmetric exclusion process, involving two species of particles driven in opposite directions on a $2 \times L$ lattice. We propose a scenario which resolves a stark discrepancy between earlier simulation data, suggesting the existence of an ordered phase, and an analytic conjecture according to which the system should revert to a disordered state in the thermodynamic limit. By analyzing the finite size effects in detail, we argue that the presence of a single, seemingly macroscopic, cluster is an intermediate stage of a comp…
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…
We study metastability and nucleation in a kinetic two-dimensional Ising model which is driven out of equilibrium by a small random perturbation of the usual dynamics at temperature T. We show that, at a mesoscopic/cluster level, a nonequilibrium potential describes in a simple way metastable states and their decay. We thus predict noise-enhanced stability of the metastable phase and resonant propagation of domain walls at low T. This follows from the nonlinear interplay between thermal and nonequilibrium fluctuations, which induces reentrant behavior of the surface tension as a function of T.…
A theoretical framework is presented for the estimation of nucleation times in systems with Brownian type dynamics. This framework is applied to a prototype system: the two-dimensional Ising model with spin-flip dynamics in an external magnetic field. Direct simulation results for the nucleation times, spanning more than four orders of magnitude, are compared with theoretical predictions. There are no free parameters; all system properties required by the theory are determined by simulations in equilibrium systems. Theoretical and simulation values are found to agree in most cases within 20%.
We investigate the nucleation, annihilation, and dynamics of kinks in a classical (1+1)-dimensional Phi^4 field theory at finite temperature. From large scale Langevin simulations, we establish that the nucleation rate is proportional to the square of the equilibrium density of kinks. We identify two annihilation time scales: one due to kink-antikink pair recombination after nucleation, the other from non-recombinant annihilation. We introduce a mesoscopic model of diffusing kinks based on ``paired'' and ``survivor'' kinks/antikinks. Analytical predictions for the dynamical time scales, as wel…
We discuss the microscopic mechanisms by which low-temperature amorphous states, such as ultrastable glasses, transform into equilibrium fluids, after a sudden temperature increase. Experiments suggest that this process is similar to the melting of crystals, thus differing from the behaviour found in ordinary glasses. We rationalize these observations using the physical idea that the transformation process takes place very close to a `hidden' equilibrium first-order phase transition, which is observed in systems of coupled replicas. We illustrate our views using simulation results for a simple…
Unlike fluids at thermal equilibrium, biomolecular mixtures in living systems can sustain nonequilibrium steady states, in which active processes modify the conformational states of the constituent molecules. Despite qualitative similarities between liquid--liquid phase separation in these systems, the extent to which the phase-separation kinetics differ remains unclear. Here we show that inhomogeneous chemical reactions can alter the nucleation kinetics of liquid--liquid phase separation in a manner that is consistent with classical nucleation theory, but can only be rationalized by introduci…
We investigate the approach to stable and metastable equilibrium in Ising models using a cluster representation. The distribution of nucleation times is determined using the Metropolis algorithm and the corresponding $ϕ^{4}$ model using Langevin dynamics. We find that the nucleation rate is suppressed at early times even after global variables such as the magnetization and energy have apparently reached their time independent values. The mean number of clusters whose size is comparable to the size of the nucleating droplet becomes time independent at about the same time that the nucleation rat…
We discuss the structure of the equation of motion that governs nucleation processes at first order phase transitions. From the underlying microscopic dynamics of a nucleating system, we derive by means of a non-equilibrium projection operator formalism the equation of motion for the size distribution of the nuclei. The equation is exact, i.e. the derivation does not contain approximations. To assess the impact of memory, we express the equation of motion in a form that allows for direct comparison to the Markovian limit. As a numerical test, we have simulated crystal nucleation from a supersa…
A phase transformation in a metastable phase can be affected when it is subjected to a high intensity ultrasound wave. In this study we determined the effect of oscillation in pressure and temperature on a phase transformation using the Gibbs droplet model in a generic format. The developed model is valid for both equilibrium and non-equilibrium clusters formed through a stationary or non-stationary process. We validated the underlying model by comparing the predicted kinetics of water droplet formation from the gas phase against experimental data in the absence of ultrasound. Our results demo…
Unravelling the composition and characteristics of gas and dust lost by asymptotic giant branch (AGB) stars is important as these stars play a vital role in the chemical life cycle of galaxies. The general hypothesis of their mass loss mechanism is a combination of stellar pulsations and radiative pressure on dust grains. However, current models simplify dust formation, which starts as a microscopic phase transition called nucleation. Various nucleation theories exist, yet all assume chemical equilibrium, growth restricted by monomers, and commonly use macroscopic properties for a microscopic …
Classical nucleation theory (CNT), linking rare nucleation events to the free energy landscape of a growing nucleus, is central to understanding phase-change kinetics in passive fluids. Nucleation in non-equilibrium systems is much harder to describe because there is no free energy, but instead a dynamics-dependent quasi-potential that typically must be found numerically. Here we extend CNT to a class of active phase separating systems governed by a minimal field-theoretic model (Active Model B+). In the small noise and supersaturation limits that CNT assumes, we compute analytically the quasi…
Recent experiments have shown how nematically-ordered tactoid shaped actin droplets can be reorganized and divided by the action of myosin molecular motors. In this paper, we consider how similar morphological changes can potentially be achieved under equilibrium conditions. Using simulations, both atomistic and continuum, and a phenomenological model, we explore how the nucleation dynamics, shape changes, and the final steady state of a nematic tactoid droplet can be modified by interactions with model adhesive colloids that mimic a myosin motor cluster. Our results provide a prescription for…
A fluid in equilibrium in a finite volume $V$ with particle number $N$ at a density $ρ= N/V$ exceeding the onset density $ρ_f $ of freezing may exhibit phase coexistence between a crystalline nucleus and surrounding fluid. Using a method suitable for the estimation of the chemical potential of dense fluids we obtain the excess free energy due to the surface of the crystalline nucleus. There is neither a need to precisely locate the interface nor to compute the (anisotropic) interfacial tension. As a test case, a soft version of the Asakura-Oosawa model for colloid polymer-mixtures is treated. …
We present a dynamical description and analysis of non-equilibrium transitions in the noisy one-dimensional Ginzburg-Landau equation for an extensive system based on a weak noise canonical phase space formulation of the Freidlin-Wentzel or Martin-Siggia-Rose methods. We derive propagating nonlinear domain wall or soliton solutions of the resulting canonical field equations with superimposed diffusive modes. The transition pathways are characterized by the nucleations and subsequent propagation of domain walls. We discuss the general switching scenario in terms of a dilute gas of propagating do…
I give an overview of rare event simulation techniques to generate dynamical pathways across high free energy barriers. The methods on which I will concentrate are the reactive flux approach, transition path sampling, (replica-exchange) transition interface sampling, partial path sampling/milestoning, and forward flux sampling. These methods have in common that they aim to simulate true molecular dynamics trajectories at a much faster rate than naive brute force molecular dynamics. The advantages and disadvantages of these methods are discussed and compared for a simple one-dimensional test sy…
The phase separation mechanism of a binary liquid mixture off-critically quenched in its miscibility gap is nucleation and growth, its homogeneous phase reaching a metastable equilibrium state. The successive stages of growth of the nucleated droplets are a diffusion-driven free growth, an intermediate regime and a coarsening by reduction of interface (Ostwald ripening or Brownian collisions induced coalescence). We have made light attenuation experiments to investigate the sedimentation in such systems. These results have given us access experimentally to two values predicted theoretically: t…
The phase field theory of crystal nucleation described in [L. Granasy, T. Borzsonyi, T. Pusztai, Phys. Rev. Lett. 88, 206105 (2002)] is applied for nucleation in hard--sphere liquids. The exact thermodynamics from molecular dynamics is used. The interface thickness for phase field is evaluated from the cross--interfacial variation of the height of the singlet density peaks. The model parameters are fixed in equilibrium so that the free energy and thickness of the (111), (110), and (100) interfaces from molecular dynamics are recovered. The density profiles predicted without adjustable paramete…
We study both analytically and numerically metastability and nucleation in a two-dimensional nonequilibrium Ising ferromagnet. Canonical equilibrium is dynamically impeded by a weak random perturbation which models homogeneous disorder of undetermined source. We present a simple theoretical description, in perfect agreement with Monte Carlo simulations, assuming that the decay of the nonequilibrium metastable state is due, as in equilibrium, to the competition between the surface and the bulk. This suggests one to accept a nonequilibrium "free-energy" at a mesoscopic/cluster level, and it ensu…
Limits of classical constitutive laws such as Fourier and Navier-Stokes equations are discovered since decades. However, the proper extensions -- generalizations of these are not unique. They differ in the underlying physical principles and in modeling capabilities. In this paper, two different theories are discussed and compared to each other, namely the kinetic theory-based Rational Extended Thermodynamics (RET) and non-equilibrium thermodynamics with internal variables (NET-IV). First, the paper starts with the case of rigid heat conductors summarizing the result achieved so far. Then a typ…
We provide an algorithm based on weighted-ensemble (WE) methods, to accurately sample systems at steady state. Applying our method to different one- and two-dimensional models, we succeed to calculate steady state probabilities of order $10^{-300}$ and reproduce Arrhenius law for rates of order $10^{-280}$. Special attention is payed to the simulation of non-potential systems where no detailed balance assumption exists. For this large class of stochastic systems, the stationary probability distribution density is often unknown and cannot be used as preknowledge during the simulation. We compar…
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…
We study the dynamical behavior of a square lattice Ising model with exchange and dipolar interactions by means of Monte Carlo simulations. After a sudden quench to low temperatures we find that the system may undergo a coarsening process where stripe phases with different orientations compete or alternatively it can relax initially to a metastable nematic phase and then decay to the equilibrium stripe phase through nucleation. We measure the distribution of equilibration times for both processes and compute their relative probability of occurrence as a function of temperature and system size.…
Nucleation is an out-of-equilibrium process, which can be strongly affected by the presence of external fields. In this letter, we report a simple extension of classical nucleation theory to systems submitted to an homogeneous shear flow. The theory involves accounting for the anisotropy of the critical nucleus formation, and introduces a shear rate dependent effective temperature. This extended theory is used to analyze the results of extensive molecular dynamics simulations, which explore a broad range of shear rates and undercoolings. At fixed temperature, a maximum in the nucleation rate i…
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…
Kinetic Turnover in the Early-Stage Nucleation of Multi-Shell Condensed Clusters
Department of Chemistry, The Hong Kong University of Science and Technology（香港科技大学化学系）；IAS Center for AI for Scientific Discoveries, The Hong Kong University of Science and Technology（香港科技大学人工智能科学发现国际高等研究院中心）
This letter reports experimental and numerical results on particle dynamics in an out-of-equilibrium granular medium. We observed two distinct types of grain motion: the well known cage motion, during which a grain is always surrounded by the same neighbors, and low probability "jumps", during which a grain moves significantly more relative to the others. These observations are similar to the results obtained for other out-of-equilibrium systems (glasses, colloidal systems, etc.). Although such jumps are extremely rare, by inhibiting them in numerical simulations we demonstrate that they play …
Rare regions, i.e., rare large spatial disorder fluctuations, can dramatically change the properties of a phase transition in a quenched disordered system. In generic classical equilibrium systems, they lead to an essential singularity, the so-called Griffiths singularity, of the free energy in the vicinity of the phase transition. Stronger effects can be observed at zero-temperature quantum phase transitions, at nonequilibrium phase transitions, and in systems with correlated disorder. In some cases, rare regions can actually completely destroy the sharp phase transition by smearing. This top…
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…
When a system undergoes a transition from a liquid to a solid phase, it passes through multiple intermediate structures before reaching the final state. However, our knowledge on the exact pathways of this process is limited, mainly due to the difficulty of realizing direct observations. Here, we experimentally study the evolution of symmetry and density for various colloidal systems during liquid-to-solid phase transitions, and visualize kinetic pathways with single-particle resolution. We observe the formation of relatively-ordered precursor structures with different symmetries, which then c…
We investigate a phase-field-crystal model for homogeneous nucleation. Instead of solving the time evolution of a density field towards equilibrium we use a String Method to identify saddle points in phase space. The saddle points allow to obtain the nucleation barrier and the critical nucleus. The advantage of using the phase-field-crystal model for this task is its ability to resolve atomistic effects. The obtained results indicate different properties of the critical nucleus compared with bulk crystals and show a detailed description of the nucleation process.
While statistical mechanics provides a comprehensive framework for the understanding of equilibrium phase behavior, predicting the kinetics of phase transformations remains a challenge. Classical nucleation theory (CNT) provides a thermodynamic framework to relate the nucleation rate to thermodynamic quantities such as pressure difference and interfacial tension through the nucleation work necessary to spawn critical nuclei. However, it remains unclear whether such an approach can be extended to the crystallization of driven melts that are subjected to mechanical stresses and flows. Here, we d…
Rare Trajectories in a Prototypical Mean-field Disordered Model: Insights into Landscape and Instantons
Duke University（杜克大学）；Institute for Cross-disciplinary Physics and Complex Systems IFISC (CSIC-UIB)（交叉物理与复杂系统研究所（CSIC-UIB））；Bocconi University（博科尼大学）；Institute for Data Science and Analytics, Bocconi University（博科尼大学数据科学与分析研究所）；Institute of Complex Systems (ISC) - CNR, Rome unit（意大利国家研究委员会复杂系统研究所罗马分部）；Sapienza Università di Roma（罗马大学）
Hypothesis: As a fluid approaches three phase coexistence, adsorption may take place by the successive formation of two intervening wetting films. The equilibrium thickness of these wetting layers is the result of a delicate balance of intermolecular forces, as dictated by an underlying interface potential. The van der Waals forces for the two variable adsorption layers may be formulated exactly from Dzyaloshinskii-Lifshitz-Pitaevskii theory, and analytical approximations may be derived that extent well beyond the validity of conventional Hamaker theory. Calculations: We consider the adsorptio…
Rare events such as nucleation processes are of ubiquitous importance in real systems. The most popular method for nonequilibrium systems, forward flux sampling (FFS), samples rare events by using interfaces to partition the whole transition process into sequence of steps along an order parameter connecting the initial and final states. FFS usually suffers from two main difficulties: low computational efficiency due to bad interface locations and even being not applicable when trapping into unknown intermediate metastable states. In the present work, we propose an approach to overcome these di…
The role of thermodynamics in deriving constitutive equations is unique, and various approaches have been developed in the last decades. In the present paper, the frameworks of Extended Irreversible Thermodynamics (EIT) and Non-Equilibrium Thermodynamics with Internal Variables (NET-IV) are discussed and compared to each other on the basis of a particular problem of rarefied gases. In this comparison, both theoretical and experimental aspects are taken into account. Eventually, an experiment by Meyer and Sessler covering a wide range of pressures and frequencies is investigated. Here, concentr…
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 report the observation of the homogenous nucleation of crystals in a dense layer of steel spheres confined between two horizontal plates vibrated vertically. Above a critical vibration amplitude, two-layer crystals with square symmetry were found to coexist in steady state with a surrounding granular liquid. By analogy to equilibrium hard sphere systems, the phase behavior can be explained through entropy maximization. However, dramatic non-equilibrium effects are present, including a significant difference in the granular temperatures of the two phases.
We study in detail the application of renormalisation theory to models of cluster aggregation and fragmentation of relevance to nucleation and growth processes. In particular, we investigate the Becker-Doring (BD) equations, originally formulated to describe and analyse non-equilibrium phase transitions, but more recently generalised to describe a wide range of physicochemical problems. We consider here rate coefficients which depend on the cluster size in a power-law fashion, but now perturbed by small amplitude random noise. Power-law rate coefficients arise naturally in the theory of surfac…
The influence of lateral adsorbate diffusion on the dynamics of the first-order phase transition in a two-dimensional Ising lattice gas with attractive nearest-neighbor interactions is investigated by means of kinetic Monte Carlo simulations. For example, electrochemical underpotential deposition proceeds by this mechanism. One major difference from adsorption in vacuum surface science is that under control of the electrode potential and in the absence of mass-transport limitations, local adsorption equilibrium is approximately established. We analyze our results using the theory of Kolmogorov…
We study numerically the behavior of RNA secondary structures under influence of a varying external force. This allows to measure the work $W$ during the resulting fast unfolding and refolding processes. Here, we investigate a medium-size hairpin structure. Using a sophisticated large-deviation algorithm, we are able to measure work distributions with high precision down to probabilities as small as $10^{-46}$. Due to this precision and by comparison with exact free-energy calculations we are able to verify the theorems of Crooks and Jarzynski. Furthermore, we analyze force-extension curves an…
A lattice model of three-state stochastic phase-coupled oscillators has been shown by Wood et al (2006 Phys. Rev. Lett. 96 145701) to exhibit a phase transition at a critical value of the coupling parameter, leading to stable global oscillations. We show that, in the complete graph version of the model, upon further increase in the coupling, the average frequency of collective oscillations decreases until an infinite-period (IP) phase transition occurs, at which point collective oscillations cease. Above this second critical point, a macroscopic fraction of the oscillators spend most of the ti…
Although many computational methods for rare event sampling exist, this type of calculation is not usually practical for general nonequilibrium conditions, with macroscopically irreversible dynamics and away from both stationary and metastable states. A novel method for calculating the time-series of the probability of a rare event is presented which is designed for these conditions. The method is validated for the cases of the Glauber-Ising model under time-varying shear flow, the Kawasaki-Ising model after a quench into the region between nucleation dominated and spinodal decomposition domin…
Supercooled water is a metastable phase of liquid water below the melting temperature. An interesting discussion recently developed on the relationship between crystallization rate and the time scales of equilibration within the liquid phase. Calculations using a coarse grained monatomic model of water, the mW model, suggested that equilibration of the liquid below the temperature of homogeneous nucleation $T_H\approx225$ K is slower than ice nucleation. Here, a 3 $μ$s long molecular dynamics simulation of the TIP4P-Ew water model is presented to investigate the relaxation properties of an ato…
