arXiv subjects

Richard K. Bowles

Publications and source records attributed to Richard K. Bowles.

At least 19 recordsLinked to original sources

arXiv2025

Glassy dynamics and a growing structural length scale in supercooled nanoparticles

We use molecular dynamics simulation to study the relationship between structure and dynamics in supercooled binary Lennard--Jones nanoparticles over a range of particle sizes. The glass transition temperature of the nanoparticles is found to be significantly lowered relative to the bulk, decreasing as $N^{-1/3}$ with decreasing particle size. This allows the nanoparticles to sample low energy states on the potential energy landscape and we are able to study their relaxation times, measured in terms of the intermediate scattering function, and their structure, measured in terms of locally favoured structures, to low temperatures. Our work shows that the growing relaxation times in the supercooled nanoparticles are coupled with the growth of physical clusters formed from favoured local structures in a way that is well described by the Random First Order Transition entropic droplet model, but with exponents that are dependent on the nanoparticle size.

cond-mat.soft↗

arXiv2024

Thermodynamics, structure and dynamics of cylindrically confined hard spheres: The role of excess helical twist

Hard spheres confined to narrow quasi-one-dimensional cylindrical channels form perfect helical structures at close packing. Here, we use molecular dynamics simulation to show that the thermodynamics, structure and dynamics of the fluid below close packing are dominated by the presence of topological defects that reverse the local twist direction of the helix. When compressed from a random, low density state, or decompressed from high density ordered states with zero excess helical twist, the system equilibrates to an achiral fluid that exhibits two heat capacity maxima along the equation of state. The low density heat capacity maximum corresponds to the onset of helix formation and the high density maximum occurs when the system rapidly loses defects in a Schottky-like anomaly. The local twist auto-correlation function in the achiral fluid exhibits a stretched exponential decay and the structural relaxation times undergo a fragile-to-strong crossover located at the high density heat capacity maximum. We also study the effect of excess helical twist by using initial starting configurations consisting of two helical domains with opposite twist directions of different lengths. This leads to the formation of topologically protected states that are characterized by the presence of loosely bound defect pairs which become more tightly bound with increasing excess helical twist. The local twist auto-correlation function in the chiral fluid decays as a power law at long times. The possible kinetic or thermodynamic origin of this topological protection is discussed.

cond-mat.soft↗

arXiv2023

Is there a Granular Potential?

Granular materials, such as sand or grain, exhibit many structural and dynamic characteristics similar to those observed in molecular systems, despite temperature playing no role in their properties. This has led to an effort to develop a statistical mechanics for granular materials that has focused on establishing an equivalent to the microcanonical ensemble and a temperature-like thermodynamic variable. Here, we expand on these ideas by introducing a granular potential into the Edwards ensemble, as an analogue to the chemical potential, and explore its properties using a simple model of a granular system. A simple kinetic Monte Carlo simulation of the model shows the effect of mass transport leading to equilibrium and how this is connected to the redistribution of volume in the system. An exact analytical treatment of the model shows that the compactivity and the ratio of the granular potential to the compactivity determine the equilibrium between two open systems that are able to exchange volume and particles, and that mass moves from high to low values of this ratio. Analysis of the granular potential shows that adding a particle to the system increases the entropy at high compactivity, but decreases the entropy at low compactivity. Finally, we demonstrate the use of a small system thermodynamics method for the measurement of granular potential differences.

cond-mat.soft↗

arXiv2021

The Influence on Crystal Nucleation of an Order-Disorder Transition among the Subcritical Clusters

Studies of nucleation generally focus on the properties of the critical cluster, but the presence of defects within the crystal lattice means that the population of nuclei necessarily evolve through a distribution of pre-critical clusters with varying degrees of structural disorder on their way to forming a growing stable crystal. To investigate the role pre-critical clusters play in nucleation, we develop a simple thermodynamic model for crystal nucleation in terms of cluster size and the degree of cluster order that allows us to alter the work of forming the pre-critical clusters without effecting the properties of the critical cluster. The steady state and transient nucleation behaviour of the system are then studied numerically, for different microscopic ordering kinetics. We find that the models exhibits a generic order-disorder transition in the pre-critical clusters. Independent of the type of ordering kinetics, increasing the accessibility of disordered pre-critical clusters decreases both the steady state nucleation rate and the nucleation lag time. Furthermore, the interplay between the free energy surface and the microscopic ordering kinetics leads to three distinct nucleation pathways.

cond-mat.soft↗

arXiv2021

Inherent Structure Landscape of Hard Spheres Confined to Narrow Cylindrical Channels

The inherent structure landscape for a system of hard spheres confined to a hard cylindrical channel, such that spheres can only contact their first and second neighbours, is studied using an analytical model that extends previous results [Phys. Rev. Lett. 115, 025702 (2015)] to provide a comprehensive picture of jammed packings over a range of packing densities. In the model, a packing is described as an arrangement of $k$ helical sections, separated by defects, that have alternating helical twist directions and where all spheres satisfy local jamming constraints. The structure of each helical section is determined by a single helical twist angle, and a jammed packing is obtained by minimizing the length of the channel per particle with respect to the $k$ helical section angles. An analysis of a small system of $N=20$ spheres shows that the basins on the inherent structure landscape associated with these helical arrangements split into a number of distinct jammed states separated by low barriers giving rise to a degree of hierarchical organization. The model accurately predicts the geometric properties of packings generated using the Lubachevsky and Stillinger compression scheme ($N=10^4$) and provides insight into the nature of the probability distribution of helical section lengths.

cond-mat.soft↗

arXiv2021

Free energy surface of two-step nucleation

We test the theoretical free energy surface (FES) for two-step nucleation (TSN) proposed by Iwamatsu [J. Chem. Phys. 134, 164508 (2011)] by comparing the predictions of the theory to numerical results for the FES recently reported from Monte Carlo simulations of TSN in a simple lattice system [James, et al., J. Chem. Phys. 150, 074501 (2019)]. No adjustable parameters are used to make this comparison. That is, all the parameters of the theory are evaluated directly for the model system, yielding a predicted FES which we then compare to the FES obtained from simulations. We find that the theoretical FES successfully predicts the numerically-evaluated FES over a range of thermodynamic conditions that spans distinct regimes of behavior associated with TSN. All the qualitative features of the FES are captured by the theory and the quantitative comparison is also very good. Our results demonstrate that Iwamatsu's extension of classical nucleation theory provides an excellent framework for understanding the thermodynamics of TSN.

cond-mat.stat-mech↗

arXiv2020

Mapping diffusivity of narrow channels into one-dimension

The diffusion of particles trapped in long narrow channels occurs predominantly in one dimension. Here, molecular dynamics simulation is used to study the inertial dynamics of two-dimensional hard disks, confined to long, narrow, structureless channels with hard walls in the no-passing regime. We show that the diffusion coefficient obtained from the mean squared displacement can be mapped onto the exact results for the diffusion of the strictly one-dimensional hard rod system through an effective occupied volume fraction obtained from either the equation of state or a geometric projection of the particle interaction diameters.

cond-mat.soft↗

arXiv2019

The effect of soft repulsive interactions on the diffusion of particles in quasi-one-dimensional channels: A hopping time approach

Fluids confined to quasi-one-dimensional channels exhibit a dynamic crossover from single file diffusion to normal diffusion as the channel becomes wide enough for particles to hop past each other. In the crossover regime, where hopping events are rare, the diffusion coefficient in the long time limit can be related to a hopping time that measures the average time it takes a particle to escape the local cage formed by its neighbours. In this work, we show that a transition state theory that calculates the free energy barrier for two particles attempting to pass each other in the small system isobaric ensemble is able to quantitatively predict the hopping time in a system of two-dimensional soft repulsive discs [$U(r_{ij})=(σ/r_{ij})^α$] confined to a hard walled channel over a range of channel radii and degrees of particle softness measured in terms of $1/α$. The free energy barrier exhibits a maximum at intermediate values of $α$ that moves to smaller values of $1/α$ (harder particles) as the channel becomes narrower. However, the presence of the maximum is only observed in the hopping times for wide channels because the interaction potential dependence of the kinetic prefactor plays an increasingly important role for narrower channels. We also begin to explore how our transition state theory approach can be used to optimize and control dynamics in confined quasi-one-dimensional fluids.

cond-mat.soft↗

arXiv2018

Phase transitions in fluctuations and their role in two-step nucleation

We consider the thermodynamic behavior of local fluctuations occurring in a stable or metastable bulk phase. For a system with three or more phases, a simple analysis based on classical nucleation theory predicts that small fluctuations always resemble the phase having the lowest surface tension with the surrounding bulk phase, regardless of the relative chemical potentials of the phases. We also identify the conditions at which a fluctuation may convert to a different phase as its size increases, referred to here as a "fluctuation phase transition" (FPT). We demonstrate these phenonena in simulations of a two dimensional lattice model by evaluating the free energy surface that describes the thermodynamic properties of a fluctuation as a function of its size and phase composition. We show that a FPT can occur in the fluctuations of either a stable or metastable bulk phase and that the transition is first-order. We also find that the FPT is bracketed by well-defined spinodals, which place limits on the size of fluctuations of distinct phases. Furthermore, when the FPT occurs in a metastable bulk phase, we show that the superposition of the FPT on the nucleation process results in two-step nucleation (TSN). We identify distinct regimes of TSN based on the nucleation pathway in the free energy surface, and correlate these regimes to the phase diagram of the bulk system. Our results clarify the origin of TSN, and elucidate a wide variety of phenomena associated with TSN, including the Ostwald step rule.

cond-mat.stat-mech↗

arXiv2017

"Swarm relaxation": Equilibrating a large ensemble of computer simulations

It is common practice in molecular dynamics and Monte Carlo computer simulations to run multiple, separately-initialized simulations in order to improve the sampling of independent microstates. Here we examine the utility of an extreme case of this strategy, in which we run a large ensemble of $M$ independent simulations (a "swarm"), each of which is relaxed to equilibrium. We show that if $M$ is of order $10^3$, we can monitor the swarm's relaxation to equilibrium, and confirm its attainment, within $\sim 10\barτ$, where $\barτ$ is the equilibrium relaxation time. As soon as a swarm of this size attains equilibrium, the ensemble of $M$ final microstates from each run is sufficient for the evaluation of most equilibrium properties without further sampling. This approach dramatically reduces the wall-clock time required, compared to a single long simulation, by a factor of several hundred, at the cost of an increase in the total computational effort by a small factor. It is also well-suited to modern computing systems having thousands of processors, and is a viable strategy for simulation studies that need to produce high-precision results in a minimum of wall-clock time. We present results obtained by applying this approach to several test cases.

cond-mat.stat-mech↗

arXiv2017

Diffusion in Quasi-One Dimensional Channels: A Small System $n,p,T,$ Transition State Theory for Hopping Times

Particles confined to a single file, in a narrow quasi-one dimensional channel, exhibit a dynamic crossover from single file diffusion to Fickian diffusion as the channel radius increases and the particles can begin to pass each other. The long time diffusion coefficient for a system in the crossover regime can be described in terms of a hopping time, which measures the time it takes for a particle to escape the cage formed by its neighbours. In this paper, we develop a transition state theory approach to the calculation of the hopping time, using the small system isobaric--isothermal ensemble to rigorously account for the volume fluctuations associated with the size of the cage. We also describe a Monte Carlo simulation scheme that can be used to calculate the free energy barrier for particle hopping. The theory and simulation method correctly predict the hopping times for a two dimensional confined ideal gas system and a system of confined hard discs over a range of channel radii, but the method breaks down for wide channels in the hard discs case, underestimating the height of the hopping barrier due to the neglect of interactions between the small system and its surroundings.

cond-mat.soft↗

arXiv2017

Vapor Condensed and Supercooled Glassy Nanoclusters

We use molecular simulation to study the structural and dynamic properties of glassy nanoclusters formed both through the direct condensation of the vapor below the glass transition temperature, without the presence of a substrate, and \textit{via} the slow supercooling of unsupported liquid nanodroplets. An analysis of local structure using Voronoi polyhedra shows that the energetic stability of the clusters is characterized by a large, increasing fraction of bicapped square antiprism motifs. We also show that nanoclusters with similar inherent structure energies are structurally similar, independent of their history, which suggests the supercooled clusters access the same low energy regions of the potential energy landscape as the vapor condensed clusters despite their different methods of formation. By measuring the intermediate scattering function at different radii from the cluster center, we find that the relaxation dynamics of the clusters are inhomogeneous, with the core becoming glassy above the glass transition temperature while the surface remains mobile at low temperatures. This helps the clusters sample the highly stable, low energy structures on the potential energy surface. Our work suggests the nanocluster systems are structurally more stable than the ultra-stable glassy thin films, formed through vapor deposition onto a cold substrate, but the nanoclusters do not exhibit the superheating effects characteristic of the ultra-stable glass states.

cond-mat.soft↗

arXiv2016

Competitive Heterogeneous Nucleation onto a Microscopic Impurity in a Potts Model

Many metastable systems can nucleate to multiple competing stable or intermediate metastable states. In this work, a Potts model, subject to external fields, is used to study the competitive nucleation of two phases attempting to grow on a microscopic impurity. Monte Carlo simulations are used to calculate the free energy surfaces for the system under different conditions, where the relative stability of the phases is adjusted by changing the interaction parameters, and the nucleation rates obtained using multicomponent transition state theory are compared with the rates measured using the survival probability method. We find that the two methods predict similar nucleation rates when the free energy barrier used in the transition state theory is defined as the work required to form a critical embryo from the metastable phase. An analysis of the free energy surfaces also reveals that the competition between the nucleating phases leads to an effective drying of the impurity which slows down the nucleation rate compared to the single phase case.

cond-mat.soft↗

arXiv2015

Free energy of formation of small ice nuclei near the Widom line in simulations of supercooled water

The ST2 interaction potential has been used in a large number of simulation studies to explore the possibility of a liquid-liquid phase transition (LLPT) in supercooled water. Using umbrella sampling Monte Carlo simulations of ST2 water, we evaluate the free energy of formation of small ice nuclei in the supercooled liquid in the vicinity of the Widom line, the region above the critical temperature of the LLPT where a number of thermodynamic anomalies occur. Our results show that in this region there is a substantial free energy cost for the formation of small ice nuclei, demonstrating that the thermodynamic anomalies associated with the Widom line in ST2 water occur in a well-defined metastable liquid phase. On passing through the Widom line, we identify changes in the free energy to form small ice nuclei that illustrate how the thermodynamic anomalies associated with the LLPT may influence the ice nucleation process.

cond-mat.stat-mech↗

arXiv2014

An orientationally ordered helical fluid phase in a quasi-one-dimensional system of confined hard spheres

We use a series of molecular dynamics simulations, and analytical theory, to demonstrate that a system of hard spheres confined to a narrow cylindrical channel exhibits a continuous phase transition from an isotropic fluid at low densities, to an orientationally ordered, but translationally disordered, helical fluid at high densities. The ordered fluid phase contains small sections of helix separated by topological defects that change the direction of the twist, altering the local chirailty. The defects break up the translational order, but the fluid develops long range orientational order. An analysis of the particle packings show that the length separation between defects controls the geometrical properties of the helical sections, including the orientation, and that pairs of defects experience a weak, but long range attraction resulting from entropic free volumes effects. These collective long range interactions overcome the restrictions on quasi-one-dimensional transitions, even though the particle-particle interaction is short ranged.

cond-mat.soft↗

arXiv2013

A Transition State Theory for Calculating Hopping Times and Diffusion in Highly Confined Fluids

Monte Carlo simulation is used to study the dynamical crossover from single file diffusion to normal diffusion in fluids confined to narrow channels. We show that the long time diffusion coefficients for a series of systems involving hard and soft interaction potentials can be described in terms of a hopping time that measures the time it takes for a particle to escape the cage formed by its neighbors in the pore. Free energy barriers for the particle hopping process are calculated and used to show that transition state theory effectively describes the hopping time for all the systems studied, over a range of pore diameters. Our work suggests that the combination of hopping times and transition state theory offers a useful and general framework to describe the dynamics of these highly confined fluids.

cond-mat.soft↗

arXiv2013

Heterogeneous Nucleation in the Low Barrier Regime

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 (from the nucleation theorem) that are in excellent agreement with direct measurements, even near the limit of stability.

cond-mat.stat-mech↗

arXiv2012

Free energy surface of ST2 water near the liquid-liquid phase transition

We carry out umbrella sampling Monte Carlo simulations to evaluate the free energy surface of the ST2 model of water as a function two order parameters, the density and a bond-orientational order parameter. We approximate the long-range electrostatic interactions of the ST2 model using the reaction-field method. We focus on state points in the vicinity of the liquid-liquid critical point proposed for this model in earlier work. At temperatures below the predicted critical temperature we find two basins in the free energy surface, both of which have liquid-like bond orientational order, but differing in density. The pressure and temperature dependence of the shape of the free energy surface is consistent with the assignment of these two basins to the distinct low density and high density liquid phases previously predicted to occur in ST2 water.

cond-mat.stat-mech↗