arXiv subjects

Nigel B. Wilding

Publications and source records attributed to Nigel B. Wilding.

At least 19 recordsLinked to original sources

arXiv2026

Free energy differences and coexistence of clathrate structures II and H via lattice-switch Monte Carlo

We introduce a simulation technique to compute the free energy difference between two hydrate structures of different stoichiometry connected to a reservoir of gas molecules at a prescribed pressure. The method permits the determination of coexistence parameters for the system when the two hydrate structures have the same number of water molecules $N_w$. The approach is based on performing isobaric Lattice Switch Monte Carlo simulations to measure free energy differences between the hydrate structures when they are either fully occupied by gas molecules, or fully empty. This measurement is combined with thermodynamic integration within an ensemble in which the number of guest molecules $N_g$ can fluctuate under the control of a chemical potential $μ_g$. We analyze the properties of the resulting constant-$N_w,μ_g,P,T$ ensemble and show how it can be used to calculate coexistence points via a thermodynamic cycle. Applying the method to argon and methane structures, we find coexistence pressures that are in good agreement overall with the available experimental data.

physics.chem-ph↗

arXiv2025

Critical surface phase behavior governs hydrophobic attraction between extended solutes

Hydrophobic interactions are central to biological self-assembly and soft matter organization, yet their microscopic origins remain debated. A key hallmark is the strengthening of attraction between hydrophobic solutes with increasing temperature, a feature often attributed to entropy changes from disrupted hydrogen bonding in water. Here we present an alternative framework based on surface phase behavior, supported by extensive molecular dynamics simulations. Using metadynamics, we quantify the solvent-mediated effective potential between nanometer-scale hydrophobic solutes in the monatomic water (mW) model, the SPCE water model, and a Lennard-Jones solvent. We develop a morphometric model which incorporates a scaling theory of critical drying, linking the range and strength of hydrophobic attraction to interfacial thermodynamics and proximity to vapor-liquid coexistence. The model reproduces the effective potential across diverse solute sizes, degrees of hydrophobicity, and thermodynamic states. Our simulations recover the inverse temperature dependence of hydrophobicity, showing it arises generically from rapid thermal expansion of the solvation shell.

cond-mat.soft↗

arXiv2024

Coarsening in Bent-core Liquid Crystals: Intermediate Splay Bend State en route to the Twist Bend Phase

We use molecular dynamics simulations to study coarsening dynamics in achiral banana-shaped bent-core liquid crystals following a quench from the high concentration polar smectic (SmX) phase to lower concentrations that favor the exotic twist-bend (TB) phase. Our novel result is the identification of an intermediate splay-bend state emerging prior to the eventual TB phase. The latter coarsens via the annihilation of {\it beta lines} which are analogous to string defects in nematic liquid crystals. Our findings are relevant for a large class of chiral systems assembled from achiral entities.

cond-mat.stat-mech↗

arXiv2024

What is the best simulation approach for measuring local density fluctuations near solvo/hydrophobes?

Measurements of local density fluctuations are crucial to characterizing the interfacial properties of equilibrium fluids. A specific case that has been well-explored involves the heightened compressibility of water near hydrophobic entities. Commonly, a spatial profile of local fluctuation strength is constructed from measurements of the mean and variance of solvent particle number fluctuations in a set of contiguous sub-volumes of the system adjacent to the solvo/hydrophobe. An alternative measure proposed by Evans and Stewart (J. Phys.: Condens. Matter 27, 194111 (2015)) defines a local compressibility profile in terms of the chemical potential derivative of the spatial number density profile. Using Grand Canonical Monte Carlo simulation, we compare and contrast the efficacy of these two approaches for a Lennard-Jones solvent at spherical and planar solvophobic interfaces, and SPC/E water at a hydrophobic spherical solute. Our principal findings are that: (i) the local compressibility profile $χ({\bf r})$ of Evans and Stewart is considerably more sensitive to variations in the strength of local density fluctuations than the spatial fluctuation profile $F({\bf r})$ and can resolve much more detailed structure; (ii) while the local compressibility profile is essentially independent of the choice of spatial discretization used to construct the profile, the spatial fluctuation profile exhibits strong systematic dependence on the size of the subvolumes on which the profile is defined. We clarify the origin and nature of this finite-size effect.

cond-mat.soft↗

arXiv2023

Sensitivity of solid phase stability to the interparticle potential range: studies of a new Lennard-Jones like model

In a recent article, Wang et al (Phys. Chem. Chem. Phys., 22, 10624 (2020)) introduced a new class of interparticle potential for molecular simulations. The potential is defined by a single range parameter, eliminating the need to decide how to truncate truly long-range interactions like the Lennard-Jones (LJ) potential. The authors explored the phase diagram for a particular value of the range parameter for which their potential is similar in shape to the LJ 12-6 potential. We have reevaluated the solid phase behaviour of this model using both Lattice Switch Monte Carlo and thermodynamic integration. In addition to finding that the boundary between hexagonal close packed (hcp) and face centred cubic (fcc) phases presented by Wang et al was calculated incorrectly, we show that owing to its finite range, the new potential exhibits several 'artifact' reentrant transitions between hcp and fcc phases. The artifact phases, which do not occur in the full (untruncated) LJ system, are also found for typically adopted forms of the truncated and shifted LJ potential. However, whilst in the latter case one can systematically investigate and correct for the effects of the finite range on the calculated phase behaviour, this is not possible for the new potential because the choice of range parameter affects the entire potential shape. Our results highlight that potentials with finite range may fail to represent the crystalline phase behaviour of systems with long-range dispersion interactions, even qualitatively.

cond-mat.stat-mech↗

arXiv2023

Partial and complete wetting of droplets of active Brownian particles

We study wetting droplets formed of active Brownian particles in contact with a repulsive potential barrier, in a wedge geometry. Our numerical results demonstrate a transition between partially wet and completely wet states, as a function of the barrier height, analogous to the corresponding surface phase transition in passive fluids. We analyse partially wet configurations characterised by a nonzero contact angle $θ$ between the droplet surface and the barrier, including the average density profile and its fluctuations. These findings are compared with two equilibrium systems: a Lennard-Jones fluid and a simple contour model for a liquid-vapour interface. We locate the wetting transition where $\cos(θ)=1$, and the neutral state where $\cos(θ)=0$. We discuss the implications of these results for possible definitions of surface tensions in active fluids.

cond-mat.stat-mech↗

arXiv2023

Grain boundary segregation and phase separation in ceria-zirconia from atomistic simulation

Doping is the most common strategy employed in the development of new and improved materials. However, predicting the effects of doping on the atomic-scale structure of a material is often difficult or limited to high-end experimental techniques. Doping can induce phase separation in a material, undermining the material's stability. A further complication is that dopant atoms can segregate to interfaces in a material such as grain boundaries (GBs), with consequences for key macroscopic properties of the material such as its conductivity. Here, we describe a computational methodology based on semi-grand canonical Monte Carlo which can be used to probe these phenomena at the atomic scale for metal oxide solid solutions. The methodology can provide precise predictions of the thermodynamic conditions at which phase separation occurs. It can also provide the segregation patterns exhibited by GBs at given conditions. We apply the methodology to one of the most important catalytic materials, ceria-zirconia. Our calculations reveal an interesting richness in the GB segregation in this system. Most GBs we examined exhibited continuous increases in Zr segregation upon Zr doping, with a concomitant reduction in the formation enthalpies of the GBs. However, a few GBs exhibited no segregation at low temperatures. We also observed evidence of first-order complexion transitions in some GBs.

cond-mat.mtrl-sci↗

arXiv2022

Understanding the physics of hydrophobic solvation

Simulations of water near extended hydrophobic spherical solutes have revealed the presence of a region of depleted density and accompanying enhanced density fluctuations.The physical origin of both phenomena has remained somewhat obscure. We investigate these effects employing a mesoscopic binding potential analysis, classical density functional theory (DFT) calculations for a simple Lennard-Jones (LJ) solvent and Grand Canonical Monte Carlo (GCMC) simulations of a monatomic water (mw) model. We argue that the density depletion and enhanced fluctuations are near-critical phenomena. Specifically, we show that they can be viewed as remnants of the critical drying surface phase transition that occurs at bulk liquid-vapor coexistence in the macroscopic planar limit, i.e.~as the solute radius $R_s\to\infty$. Focusing on the radial density profile $ρ(r)$ and a sensitive spatial measure of fluctuations, the local compressibility profile $χ(r)$, our binding potential analysis provides explicit predictions for the manner in which the key features of $ρ(r)$ and $χ(r)$ scale with $R_s$, the strength of solute-water attraction $\varepsilon_{sf}$, and the deviation from liquid-vapor coexistence of the chemical potential, $δμ$. These scaling predictions are confirmed by our DFT calculations and GCMC simulations. As such our theory provides a firm basis for understanding the physics of hydrophobic solvation.

cond-mat.soft↗

arXiv2022

Multilevel simulation of hard-sphere mixtures

We present a multilevel Monte Carlo simulation method for analysing multi-scale physical systems via a hierarchy of coarse-grained representations, to obtain numerically-exact results, at the most detailed level. We apply the method to a mixture of size-asymmetric hard spheres, in the grand canonical ensemble. A three-level version of the method is compared with a previously-studied two-level version. The extra level interpolates between the full mixture and a coarse-grained description where only the large particles are present -- this is achieved by restricting the small particles to regions close to the large ones. The three-level method improves the performance of the estimator, at fixed computational cost. We analyse the asymptotic variance of the estimator, and discuss the mechanisms for the improved performance.

cond-mat.stat-mech↗

arXiv2022

Measures of Fluctuations for a Liquid Near Critical Drying

We investigate density fluctuations in a liquid close to a solvophobic substrate at which a surface critical drying transition occurs. Using classical density functional theory, we determine three measures of the spatial extent and strength of the fluctuations, i.e., the local compressibility $χ_μ(z)$, the local thermal susceptibility $χ_T(z)$ and the reduced density $χ_*(z)$; $z$ is the distance from the substrate. Whilst the first measure is frequently used, the second and third were introduced very recently by Eckert et.al., Phys. Rev. Lett. 125, 268004 (2020). For state points in the critical drying regime, all three measures, each scaled by its bulk value, exhibit very similar forms and the ratio of $χ_T(z)$ to $χ_μ(z)$, for fixed $z$ in the vapour-liquid transition region, is constant. Using a scaling treatment of surface thermodynamics we show that such behaviour is to be expected on general grounds.

cond-mat.stat-mech↗

arXiv2022

Equilibrium phases and domain growth kinetics of calamitic liquid crystals

The anisotropic shape of calamitic LC particles results in distinct energy values when nematogens are placed side-by-side or end-to-end. The energy anisotropy governed by parameter K' has deep consequences on equilibrium & non-equilibrium properties. Using GB model, which shows Nm & low temperature Sm order, we undertake large-scale MC & MD simulations to probe effect of K' on the equilibrium phase diagram & the non-equilibrium domain growth following a quench in the temperature T (coarsening). There are 2 transitions in the model, I->Nm at Tc1 & Nm->Sm at Tc2 Tc1->T<Tc2) that we consider has SmB order with a hexatic arrangement of the LC molecules in the layers. Coarsening in this phase exhibits a striking two-time-scale scenario: first the LC molecules align & develop orientational order, followed by emergence of characteristic layering along with the hexatic bond-orientational-order within layers. Consequently, the growth follows the LAC law L(t)~t^0.5 at early times & then shows a sharp crossover to a slower growth regime at later times. Our observations strongly suggest L(t)~t^0.25 in this regime. Interestingly, the correlation function shows dynamical scaling in both the regimes & the scaling function is universal. The dynamics is also robust with respect to changes in K', but the smecticity is more pronounced at larger values. Further, the early-time dynamics is governed by string defects, while the late-time evolution is dictated by interfacial defects. We believe this scenario is generic to Sm phase even with other kinds of local order within Sm layers.

cond-mat.stat-mech↗

arXiv2022

Density depletion and enhanced fluctuations in water near hydrophobic solutes: identifying the underlying physics

We investigate the origin of the density depletion and enhanced density fluctuations that occur in water in the vicinity of an extended hydrophobic solute. We argue that both phenomena are remnants of the critical drying surface phase transition that occurs at liquid-vapor coexistence in the macroscopic planar limit, ie. as the solute radius $R_s\to\infty$. Focusing on the density profile $ρ(r)$ and a sensitive spatial measure of fluctuations, the local compressibility profile $χ(r)$, we develop a scaling theory which expresses the extent of the density depletion and enhancement in compressibility in terms of $R_s$, the strength of solute-water attraction $\varepsilon_s$, and the deviation from liquid-vapor coexistence $δμ$. Testing the predictions against results of classical density functional theory for a simple solvent and Grand Canonical Monte Carlo simulations of a popular water model, we find that the theory provides a firm physical basis for understanding how water behaves at a hydrophobe.

cond-mat.soft↗

arXiv2021

Wetting transition of active Brownian particles on a thin membrane

We study non-equilibrium analogues of surface phase transitions in a minimal model of active particles in contact with a purely repulsive potential barrier that mimics a thin porous membrane. Under conditions of bulk motility-induced phase separation, the interaction strength $\varepsilon_w$ of the barrier controls the affinity of the dense phase for the barrier region. We uncover clear signatures of a wetting phase transition as $\varepsilon_w$ is varied. In common with its equilibrium counterpart, the character of this transition depends on the system dimensionality: a continuous transition with large density fluctuations and gas bubbles is uncovered in 2d while 3d systems exhibit a sharp transition absent of large correlations.

cond-mat.stat-mech↗

arXiv2021

Critical point for de-mixing of binary hard spheres

We use a two-level simulation method to analyse the critical point associated with demixing of binary hard sphere mixtures. The method exploits an accurate coarse-grained model with two-body and three-body effective interactions. Using this model within the two-level methodology allows computation of properties of the full (fine-grained) mixture. The critical point is located by computing the probability distribution for the number of large particles in the grand canonical ensemble, and matching to the universal form for the $3d$ Ising universality class. The results have a strong and unexpected dependence on the size ratio between large and small particles, which is related to three-body effective interactions, and the geometry of the underlying hard sphere packings.

cond-mat.stat-mech↗

arXiv2020

Phase separation and multibody effects in three-dimensional active Brownian particles

Simulation studies of the phase diagram of repulsive active Brownian particles in three dimensions reveal that the region of motility-induced phase separation between a high and low density phase is enclosed by a region of gas-crystal phase separation. Near-critical loci and structural crossovers can additionally be identified in analogy with simple fluids. Motivated by the striking similarity to the behaviour of equilibrium fluids with short-ranged pair-wise attractions, we show that a direct mapping to pair potentials in the dilute limit implies interactions that are insufficiently attractive to engender phase separation. Instead, this is driven by the emergence of multi-body effects associated with particle caging that occurs at sufficiently high number density. We quantify these effects via information-theoretical measures of $n$-body effective interactions extracted from the configurational structure.

cond-mat.stat-mech↗

arXiv2019

A unified description of hydrophilic and superhydrophobic surfaces in terms of the wetting and drying transitions of liquids

Clarifying the factors that control the contact angle of a liquid on a solid substrate is a long-standing scientific problem pertinent across physics, chemistry and materials science. Progress has been hampered by the lack of a comprehensive and unified understanding of the physics of wetting and drying phase transitions. Using various theoretical and simulational techniques applied to realistic fluid models, we elucidate how the character of these transitions depends sensitively on both the range of fluid-fluid and substrate-fluid interactions and the temperature. Our calculations uncover previously unrecognised classes of surface phase diagram which differ from that established for simple lattice models and often assumed to be universal. The differences relate both to the topology of the phase diagram and to the nature of the transitions, with a remarkable feature being a difference between drying and wetting transitions which persists even in the approach to the bulk critical point. Most experimental and simulational studies of liquids at a substrate belong to one of these previously unrecognised classes. We predict that while there appears to be nothing particularly special about water with regard to its wetting and drying behavior, superhydrophobic behavior should be more readily observable in experiments conducted at high temperatures than at room temperature.

cond-mat.stat-mech↗

arXiv2019

Correction of coarse-graining errors by a two-level method: application to the Asakura-Oosawa model

We present a method that exploits self-consistent simulation of coarse-grained and fine-grained models, in order to analyse properties of physical systems. The method uses the coarse-grained model to obtain a first estimate of the quantity of interest, before computing a correction by analysing properties of the fine system. We illustrate the method by applying it to the Asakura-Oosawa (AO) model of colloid-polymer mixtures. We show that the liquid-vapour critical point in that system is affected by three-body interactions which are neglected in the corresponding coarse-grained model. We analyse the size of this effect and the nature of the three-body interactions. We also analyse the accuracy of the method, as a function of the associated computational effort.

cond-mat.stat-mech↗

arXiv2018

A simulated annealing approach to the student-project allocation problem

We describe a solution to the student-project allocation problem using simulated annealing. The problem involves assigning students to projects, where each student has ranked a fixed number of projects in order of preference. Each project is offered by a specific supervisor (or supervisors), and the goal is to find an optimal matching of students to projects taking into account the students' preferences, the constraint that only one student can be assigned to a given project, and the constraint that supervisors have a maximum workload. We show that when applied to a real dataset from a university physics department, simulated annealing allows the rapid determination of high quality solutions to this allocation problem. The quality of the solution is quantified by a satisfaction metric derived from empirical student survey data. Our approach provides high quality allocations in a matter of minutes that are as good as those found previously by the course organizer using a laborious trial-and-error approach. We investigate how the quality of the allocation is affected by the ratio of the number of projects offered to the number of students and the number of projects ranked by each student. We briefly discuss how our approach can be generalized to include other types of constraints and discuss its potential applicability to wider allocation problems.

cs.AI↗