arXiv subjects

Patrick B. Warren

Publications and source records attributed to Patrick B. Warren.

At least 19 recordsLinked to original sources

arXiv2026

Self-Generated Electric Fields in Polyelectrolyte Gradients Increase Microparticle Transport

There are many situations in nature and industry where small particles are exposed to gradients of charged polymers, such as enzymes in biological gradients of DNA or RNA, virus particles in respiratory droplets, and colloidal particles in stratifying paint layers. Here, we study the phoretic propulsion of charged microparticles in a polyelectrolyte gradient. We theoretically predict the emergence of a macroscopic electric field from charge-separation dynamics in a polyelectrolyte gradient under a continuous diffusive driving force. We confirm the presence of this self-generated electric field experimentally and show that it significantly increases the phoretic velocity of the microparticles. Finally, for high molecular weight polyelectrolytes we observe that propulsion becomes gradient-independent, consistent with diffusiophoretic predictions for asymmetric electrolytes. Our results show that self-generated electric fields in polyelectrolyte gradients can enhance microparticle transport, with potential applicability wherever charged species of different mobility are continuously driven out of equilibrium.

cond-mat.soft↗

arXiv2026

Approximate additivity in the solvent-mediated potential of mean force for ultrasoft particle systems

In the infinite dilution limit, we show that the solvent-mediated potential of mean force (PMF) between solutes, extracted from the hypernetted-chain (HNC) closure of the Ornstein-Zernike equations, can expressed as a convolution between solute-specific generalised excluded volume functions. In the limit of a structureless solvent of point particles and hard core solutes, this recovers the exact Asakura-Oosawa depletion potential as the overlap between excluded volume spheres. The methodology can be deployed for ultrasoft particle systems such as those encountered in dissipative particle dynamics (DPD), where the solvent-mediated PMF can be recovered with considerable accuracy. These results confirm that in coarse-grained molecular DPD simulations the parametrisation of the non-bonded repulsions is sensitive to the assumed intramolecular bond lengths if they are smaller than the range of the DPD potential, due to the overlap of the soft excluded volume functions.

cond-mat.soft↗

arXiv2025

Simple models for the trapping of charged particles and macromolecules by diffusiophoresis in salt gradients

We study the trapping of charged particles and macromolecules (such as DNA) in salt gradients in aqueous solutions. The source for the salt gradient can be as simple as a dissolving ionic crystal, as shown by McDermott et al. [Langmuir 28, 15491 (2012)]. Trapping is due to a competition between localisation due to diffusiophoresis in the salt gradient, and spreading out by diffusion. The size of the trap is typically 1 to 100 micrometres. We further predict that at steady state, the particle (macromolecule) number density is a power law of the salt concentration, with an exponent that is the ratio of the diffusiophoretic mobility to the diffusion coefficient of the trapped species. This ratio increases with size and typically becomes much greater than 1 for particles or macromolecules with hydrodynamic radii of hundreds of nanometres and above. Thus large particles or macromolecules are easily caught and trapped at steady state by salt gradients.

cond-mat.soft↗

arXiv2025

Why life is hot

The process of evolution by natural selection leads to phenotypes of increasing fitness. For cellular chemical reaction networks, this means optimising a variety of fitness functions such as robustness, precision, or sensitivity to external stimuli. We argue that these diverse goals can be achieved by a versatile, generic mechanism: coupling chemical reaction networks to reservoirs that are strongly out of equilibrium. Using theory and numerics we show that this mechanism of optimization comes at the price of significant heat dissipation. We compute the heat flux caused by kinetic proofreading in {\it Escherichia coli} and show that it constitutes a significant fraction of the total heat flux experimentally measured in this model organism. We then demonstrate that the degree of optimality achievable saturates, and that Nature appears to operate near saturation despite high energetic costs. We conclude that `life is hot' largely because of the need for a versatile mechanism to optimise a variety of fitness functions.

cond-mat.soft↗

arXiv2025

Wertheim association theory for ion pairing in electrolytes: effect of neutral clusters

We address the problem of the vapor-liquid phase transition in the restricted primitive model (RPM) using Wertheim's statistical associating fluid theory to capture the effects of ion pairing which dominate the low-temperature vapor phase. For this we employ a reference system in which ion-pairing is suppressed by a judicious modification of the interaction between unlike charges from 1/r to erf(kappa r)/r, where kappa is a state-dependent parameter chosen so that the Helmholtz free energy A is at a null point (dA/d(kappa) = 0). Unlike the original RPM, this reference fluid admits real solutions to the hypernetted-chain (HNC) closure of the Ornstein-Zernike equations over a wide range of densities and temperatures. In the present study, we go beyond previous work [M. Li, Ph.D. thesis, University of Manchester (2011)] to allow for isodesmic assembly of ion pairs into neutral clusters. We find this has the potential to improve significantly the agreement with the Monte-Carlo results for the RPM vapor phase boundary. We can also match recent results on anomalous underscreening in the RPM [Härtel et al., Phys. Rev. Lett. 130, 108202 (2023)] assuming that only the free ions contribute to the screening length.

cond-mat.soft↗

arXiv2025

Poisson-Nernst-Planck charging dynamics of an electric double layer capacitor: symmetric and asymmetric binary electrolytes

A parallel plate capacitor containing an electrolytic solution is the simplest model of a supercapacitor, or electric double layer capacitor. Using both analytical and numerical techniques, we solve the Poisson-Nernst-Planck equations for such a system, describing the mean-field charging dynamics of the capacitor, when a constant potential difference is abruptly applied to its plates. Working at constant total number of ions, we focus on the physical processes involved in the relaxation and, whenever possible, give its functional shape and exact time constants. We first review and study the case of a symmetric binary electrolyte, where we assume the two ionic species to have the same charges and diffusivities. We then relax these assumptions and present results for a generic strong (i.e. fully dissociated) binary electrolyte. At low electrolyte concentration, the relaxation is simple to understand, as the dynamics of positive and negative ions appear decoupled. At higher electrolyte concentration, we distinguish several regimes. In the linear regime (low voltages), relaxation is multi-exponential, it starts by the build-up of the equilibrium charge profile and continues with neutral mass diffusion, and the relevant time scales feature both the average and the Nernst-Hartley diffusion coefficients. In the purely nonlinear regime (intermediate voltages), the initial relaxation is slowed down exponentially due to increased capacitance, while bulk effects become more and more evident. In the fully nonlinear regime (high voltages), the dynamics of charge and mass are completely entangled and, asymptotically, the relaxation is linear in time. We finally discuss non-ideal behavior in real capacitors and provide conditions for which mean-field is expected to hold.

cond-mat.soft↗

arXiv2025

Charging dynamics of electric double layer nanocapacitors in mean-field

An electric double layer capacitor (EDLC) stores energy by modulating the spatial distribution of ions in the electrolytic solution that it contains. We determine the mean-field time scales for planar EDLC relaxation to equilibrium, after a potential difference is applied. We tackle first the fully symmetric case, where positive and negative ionic species have same valence and diffusivity, and then the general, more complex, asymmetric case. Depending on applied voltage and salt concentration, different regimes appear, revealing a remarkably rich phenomenology relevant for nanocapacitors.

physics.chem-ph↗

arXiv2025

Critical inertia for particle capture is determined by surface geometry at forward stagnation point

Aerosols are ubiquitous, and particle capture from particle-laden air as it flows past an obstacle is of widespread practical importance. Neglecting diffusion, previous work has shown that for a smooth curved surface in both Stokes flow and inviscid flow, only particles with inertia above a threshold value (quantified by the nondimensional Stokes number) collide with the surface. Here we show that the critical Stokes number decreases with increasing Reynolds number of the air flow, and the mechanism behind this threshold is the same at all finite Reynolds numbers but becomes qualitatively different in the limit of infinite Reynolds number (inviscid flow). In addition we show that in the latter case (inviscid flow) the threshold is set solely by the flow near the stagnation point, whereas at finite Reynolds numbers the threshold also depends on the flow far from the stagnation point. The threshold also depends on obstacle geometry and we show that fibers whose cross section is flattened along the flow direction have greater size selectivity than fibers with a circular cross section.

physics.flu-dyn↗

arXiv2025

Diffusive evaporation dynamics in polymer solutions is ubiquitous

Recent theory and experiments have shown how the buildup of a high-concentration polymer layer at a one-dimensional solvent-air interface can lead to an evaporation rate that scales with time as $t^{-1/2}$ and that is insensitive to the ambient humidity. Using phase field modelling we show that this scaling law constitutes a naturally emerging robust regime, Diffusion-Limited Evaporation (DLE). This regime dominates the dynamical state diagram of the system, which also contains regions of constant and arrested evaporation, confirming and extending understanding of recent experimental observations and theoretical predictions. We provide a theoretical argument to show that the scaling observed in the DLE regime occurs for a wide range of parameters, and our simulations predict that it can occur in two-dimensional geometries as well. Finally, we discuss possible extensions to more complex systems.

cond-mat.soft↗

arXiv2024

Renormalisation group theory applied to $\ddot{x}+\dot{x}+x^2=0$

The titular ordinary differential equation (ODE) is encountered in the theory of on-axis inertial particle capture by a blunt stationary collector at a viscous-flow stagnation point. Phase space for the ODE divides into two attractor basins, representing particle trajectories which do or do not collide with the collector in a finite time. Written as $\ddot{x} + \dot{x} + εx^2 = 0$, we formulate the renormalisation group (RG) amplitude equations for this problem and argue that the critical trajectory which separates the attractor basins corresponds to a trivial but exact solution of these, and can therefore be extracted as a power series in $ε$. We show how this can be used to find the cross-over between capture and non-capture as a function of distance from the stagnation point, for a particle released into the flow with no initial acceleration. This cross-over, previously only computable by numerical integration of the ODE, can therefore be expressed as a (numerically) convergent series with rational terms.

math-ph↗

arXiv2024

Salt solutions with two or more salts generate ion currents analogous to magnetic field lines

A gradient of a single salt in a solution generates an electric field, but not a current. Recent theoretical work by one of us [Phys. Rev. Lett. 24, 248004 (2020)] showed that the Nernst-Planck equations imply that crossed gradients of two or more different salts generate ion currents. These currents in solution have associated non-local electric fields. Particle motion driven by these non-local fields has recently been observed in experiment by Williams et al. [Phys. Rev. Fluids 9, 014201 (2024)]; a phenomenon which was dubbed action-at-a-distance diffusiophoresis. Here we use a magnetostatic analogy to show that in the far-field limit, these non-local currents and electric fields both have the functional form of the magnetic field of a magnetic dipole, decaying as r^(-d) in d = 2 and d = 3 dimensions. These long-ranged electric fields are generated entirely within solutions and have potential practical applications since they can drive both electrophoretic motion of particles, and electro-osmotic flows. The magnetostatic analogy also allows us to import tools and ideas from classical electromagnetism, into the study of multicomponent salt solutions.

cond-mat.soft↗

arXiv2024

Polarisable soft solvent models with applications in dissipative particle dynamics

We critically examine a broad class of explicitly polarisable soft solvent models aimed at applications in dissipative particle dynamics. We obtain the dielectric permittivity using the fluctuating box dipole method in linear response theory, and verify the models in relation to several test cases including demonstrating ion desorption from an oil-water interface due to image charge effects. We additionally compute the Kirkwood factor and find it uniformly lies in the range gK approx 0.7-0.8, indicating that dipole-dipole correlations are not negligible in these models. This is supported by measurements of dipole-dipole correlation functions. As a consequence, Onsager theory over-predicts the dielectric permittivity by approximately 20-30 percent. On the other hand, the mean square molecular dipole moment can be accurately estimated with a first-order Wertheim perturbation theory.

cond-mat.soft↗

arXiv2023

Colloidal diffusiophoresis in crossed electrolyte gradients: experimental demonstration of an 'action at a distance' effect predicted by the Nernst-Planck equations

In an externally imposed electrolyte (salt) concentration gradient, charged colloids drift at speeds of order one micrometre per second. This phenomenon is known as diffusiophoresis. In systems with multiple salts and 'crossed' salt gradients, a nonlocal component of the electric field associated with a circulating (solenoidal) ion current can arise. This is in addition to the conventional local component that depends only on the local salt gradients. Here we report experimental observations verifying the existence of this nonlocal contribution. To our knowledge this is the first observation of nonlocal diffusiophoresis. The current develops quasi-instantaneously on the time scale of salt diffusion. Therefore, in systems with multiple salts and crossed salt gradients, one can expect a nonlocal contribution to diffusiophoresis which is dependent on the geometry of the system as a whole and appears as a kind of instantaneous 'action-at-a-distance' effect. The interpretation is aided by a magnetostatic analogy. Our experiments are facilitated by a judicious particle-dependent choice of salt (potassium acetate) for which the two local contributions to diffusiophoresis almost cancel, effectively eliminating conventional diffusiophoresis. This enables us to clearly identify the novel, nonlocal effect and may be useful in other contexts, for example in sorting particle mixtures.

cond-mat.soft↗

arXiv2023

Sliding friction in the hydrodynamic lubrication regime for a power-law fluid

A scaling analysis is undertaken for the load balance in sliding friction in the hydrodynamic lubrication regime, with a particular emphasis on power-law shear-thinning typical of a structured liquid. It is argued that the shear-thinning regime is mechanically unstable if the power-law index n < 1/2, where n is the exponent that relates the shear stress to the shear rate. Consequently the Stribeck (friction) curve should be discontinuous, with possible hysteresis. Further analysis suggests that normal stress and flow transience (stress overshoot) do not destroy this basic picture, although they may provide stabilising mechanisms at higher shear rates. Extensional viscosity is also expected to be insignificant unless the Trouton ratio is large. A possible application to shear thickening in non-Brownian particulate suspensions is indicated.

cond-mat.soft↗

arXiv2023

Gap-Dependent Hydrodynamic Lubrication in Conformal Contacts

We show that the hydrodynamic lubrication of contacting conformal surfaces with a typical texture height gives rise to a universal behaviour in the Stribeck curve in which the friction coefficient shows an anomalous power-law dependence on the Sommerfeld number, $μ\sim S^{2/3}$. When the gap height drops below the `texture length scale', deviations from $S^{2/3}$ occur, which may resemble the onset of elasto-hydrodynamic and mixed lubrication. Within this framework, we analyse literature data for oral processing and find $S^{2/3}$ scaling with deviations consistent with measured lengthscales.

cond-mat.soft↗

arXiv2023

Anomalous Scaling for Hydrodynamic Lubrication of Conformal Surfaces

The hydrodynamic regime of the Stribeck curve giving the friction coefficient $μ$ as a function of the dimensionless relative sliding speed (the Sommerfeld number, $S$) of two contacting non-conformal surfaces is usually considered trivial, with $μ\sim S$. We predict that for conformal surfaces contacting over large areas, a combination of independent length scales gives rise to a universal power-law with a non-trivial exponent, $μ\sim S^{2/3}$, for a thick lubrication film. Deviations as the film thins (decreasing $S$) may superficially resemble the onset of elastohydrodynamic lubrication, but are due to a crossover between hydrodynamic regimes. Our experiments as well as recent measurements of chocolate lubrication confirm these predictions.

cond-mat.soft↗

arXiv2022

Partial osmotic pressures of ions in electrolyte solutions

The concept of the partial osmotic pressure of ions in an electrolyte solution is critically examined. In principle these can be defined by introducing a solvent-permeable wall and measuring the force per unit area which can certainly be attributed to individual ions. Here I demonstrate that although the total wall force balances the bulk osmotic pressure as required by mechanical equilibrium, the individual partial osmotic pressures are extra-thermodynamic quantities dependent on the electrical structure at the wall, and as such they resemble attempts to define individual ion activity coefficients. The limiting case where the wall is a barrier to only one species of ion is also considered, and with ions on both sides the classic Gibbs-Donnan membrane equilibrium is recovered thus providing a unifying treatment. The analysis can be extended to illustrate how the electrical state of the bulk is affected by the nature of the walls and the sample handling history, thus supporting the 'Gibbs-Guggenheim uncertainty principle' (the notion that the electrical state is unmeasurable and usually accidentally determined). Since this uncertainty is conferred also onto individual ion activities, it has implications for the current (2002) IUPAC definition of pH.

cond-mat.soft↗

arXiv2018

Trajectory reweighting for non-equilibrium steady states

Modern methods for sampling rugged landscapes in state space mainly rely on knowledge of the relative probabilities of microstates, which is given by the Boltzmann factor for equilibrium systems. In principle, trajectory reweighting provides an elegant way to extend these algorithms to non-equilibrium systems, by numerically calculating the relative weights that can be directly substituted for the Boltzmann factor. We show that trajectory reweighting has many commonalities with Rosenbluth sampling for chain macromolecules, including practical problems which stem from the fact that both are iterated importance sampling schemes: for long trajectories the distribution of trajectory weights becomes very broad and trajectories carrying high weights are infrequently sampled, yet long trajectories are unavoidable in rugged landscapes. For probing the probability landscapes of genetic switches and similar systems, these issues preclude the straightforward use of trajectory reweighting. The analogy to Rosenbluth sampling suggests though that path ensemble methods such as PERM (pruned-enriched Rosenbluth method) could provide a way forward.

cond-mat.stat-mech↗