## Publications

205 results found

Mendes J, Russo A, Perez SP,
et al., 2021, A finite-volume scheme for gradient-flow equations with non-homogeneous diffusion, *Computers & Mathematics with Applications*, Vol: 89, Pages: 150-162, ISSN: 0898-1221

We develop a first- and second-order finite-volume scheme to solve gradient flow equations with non-homogeneous properties, obtained in the framework of dynamical-density functional theory. The scheme takes advantage of an upwind approach for the space discretization to ensure positivity of the density under a CFL condition and decay of the discrete free energy. Our computational approach is used to study several one- and two-dimensional systems, with a general free-energy functional accounting for external fields and inter-particle potentials, and placed in non-homogeneous thermal baths characterized by anisotropic, space-dependent and time-dependent properties.

Yatsyshin P, Kalliadasis S, 2021, Surface nanodrops and nanobubbles: a classical density functional theory study, *Journal of Fluid Mechanics*, Vol: 913, Pages: 1-16, ISSN: 0022-1120

We present a fully microscopic study of the interfacial thermodynamics of nanodrops and nanobubbles, adsorbed on flat substrates with first-order wetting. We show that both nanodrops and nanobubbles are thermodynamically accessible in regions, demarcated by the spinodals of planar wetting films, with nanobubbles occupying a relatively bigger portion of the phase space. While nanodrops can be described as near-spherical caps of Laplace radius, the radius of nanobubbles is very different from the Laplace value. Additionally, nanobubbles are accompanied by a thin gas film adsorbed on the substrate. By computing the interface binding potential, we relate the sphericity of nanodrops to the thin–thick liquid film coexistence (prewetting transition), whereas nanobubble shapes are determined only by the decay of the fluid–substrate forces.

Duran-Olivencia M, Kalliadasis S, 2021, More than a year after the onset of the CoVid-19 pandemic in the UK: lessons learned from a minimalistic model capturing essential features including social awareness and policy making, Publisher: MedRxiv

The number of new daily SARS-CoV-2 infections experienced an abrupt increase during the last quarter of 2020 in almost every European country. The phenomenological explanation offered was a new mutation of the virus, first identified in the UK. We use publicly available data in combination with a time-delayed controlled SIR model, which captures the effects of preventive measures and concomitant social response on the spreading of the virus. The model, which has a unique transmission rate, enables us to reproduce the waves of infection occurred in the UK. This suggests that the new SARS-CoV-2 UK variant is as transmissible as previous strains. Our findings reveal that the sudden surge in cases was in fact related to the relaxation of preventive measures and social awareness. We also simulate the combined effects of restrictions and vaccination campaigns in 2021, demonstrating that lockdown policies are not fully effective to flatten the curve; fully effective mitigation can only be achieved via a vigorous vaccination campaign. As a matter of fact, incorporating recent data about vaccine efficacy, our simulations advocate that the UK might have overcome the worse of the CoVid-19 pandemic, provided that the vaccination campaign maintains a rate of approximately 140k jabs per day.

Russo A, Perez SP, Durán-Olivencia MA,
et al., 2021, A finite-volume method for fluctuating dynamical density functional theory, *Journal of Computational Physics*, Vol: 428, ISSN: 0021-9991

We introduce a finite-volume numerical scheme for solving stochastic gradient flow equations. Such equations are of crucial importance within the framework of fluctuating hydrodynamics and dynamic density functional theory. Our proposed scheme deals with general free-energy functionals, including, for instance, external fields or interaction potentials. This allows us to simulate a range of physical phenomena where thermal fluctuations play a crucial role, such as nucleation and other energy-barrier crossing transitions. A positivity-preserving algorithm for the density is derived based on a hybrid space discretization of the deterministic and the stochastic terms and different implicit and explicit time integrators. We show through numerous applications that not only our scheme is able to accurately reproduce the statistical properties (structure factor and correlations) of physical systems, but also allows us to simulate energy barrier crossing dynamics, which cannot be captured by mean-field approaches.

Duran-Olivencia M, Kalliadasis S, 2021, Understanding soaring corona virus cases and the effect of contagion policies in the UK, Publisher: MedRxiv

The number of new daily SARS-CoV-2 infections is frantically risingin almost every country of the EU. The phenomenological explanationoffered is a new mutation of the virus, first identified in the UK.We use publicly available data in combination with a controlled SIRmodel, which captures the effects of preventive measures on the activecases, to show that the current wave of infections is consistentwith a single transmission rate. This suggests that the new SARSCoV-2 variant is as transmissible as previous strains. Our findingsindicate that the relaxation of preventive measures is closely relatedwith the ongoing surge in cases. We simulate the effects of newrestrictions and vaccination campaigns in 2021, demonstrating thatlockdown policies are not fully effective to flatten the curve. For effectivemitigation, it is critical that the public keeps on high alert untilvaccination reaches a critical threshold.

Carrillo JA, Castro MJ, Kalliadasis S,
et al., 2021, High-order well-balanced finite-volume schemes for hydrodynamic Equations with nonlocal free energy, *SIAM Journal on Scientific Computing*, Vol: 43, Pages: A828-A858, ISSN: 1064-8275

We propose high-order well-balanced finite-volume schemes for a broad class of hydrodynamic systems with attractive-repulsive interaction forces and linear and nonlinear damping. Our schemes are suitable for free energies containing convolutions of an interaction potential with the density, which are essential for applications such as the Keller--Segel model, more general Euler--Poisson systems, or dynamic-density functional theory. Our schemes are also equipped with a nonnegative-density reconstruction which allows for vacuum regions during the simulation. We provide several prototypical examples from relevant applications highlighting the benefit of our algorithms and also elucidate some of our analytical results.

Russo A, Duran-Olivencia MA, Yatsyshin P,
et al., 2020, Memory effects in fluctuating dynamic density-functional theory: theory and simulations, *Journal of Physics A: Mathematical and Theoretical*, Vol: 53, ISSN: 1751-8113

This work introduces a theoretical framework to describe the dynamics of reacting multi-species fluid systems in-and-out of equilibrium. Our starting point is the system of generalised Langevin equations which describes the evolution of the positions and momenta of the constituent particles. One particular difficulty that this system of generalised Langevin equations exhibits is the presence of a history-dependent (i.e. non-Markovian) term, which in turn makes the system's dynamics dependent on its own past history. With the appropriate definitions of the local number density and momentum fields, we are able to derive a non-Markovian Navier–Stokes-like system of equations constituting a generalisation of the Dean–Kawasaki model. These equations, however, still depend on the full set of particles phase-space coordinates. To remove this dependence on the microscopic level without washing out the fluctuation effects characteristic of a mesoscopic description, we need to carefully ensemble-average our generalised Dean–Kawasaki equations. The outcome of such a treatment is a set of non-Markovian fluctuating hydrodynamic equations governing the time evolution of the mesoscopic density and momentum fields. Moreover, with the introduction of an energy functional which recovers the one used in classical density-functional theory and its dynamic extension (DDFT) under the local-equilibrium approximation, we derive a novel non-Markovian fluctuating DDFT (FDDFT) for reacting multi-species fluid systems. With the aim of reducing the fluctuating dynamics to a single equation for the density field, in the spirit of classical DDFT, we make use of a deconvolution operator which makes it possible to obtain the overdamped version of the non-Markovian FDDFT. A finite-volume discretization of the derived non-Markovian FDDFT is then proposed. With this, we validate our theoretical framework in-and-out-of-equilibrium by comparing results against atomistic simulations. Fi

Ruyer-Quil C, Trevelyan P, Giorgiutti-Dauphiné F,
et al., 2020, Modelling film flows down a fibre – ERRATUM, *Journal of Fluid Mechanics*, Vol: 890, ISSN: 0022-1120

[Erratum]

Carrillo de la Plata JA, Kalliadasis S, Perez Perez S,
et al., 2020, Well-balanced finite volume schemes for hydrodynamic equations with general free energy, *SIAM: Multiscale Modeling and Simulation*, Vol: 18, Pages: 502-541, ISSN: 1540-3459

Well-balanced and free energy dissipative first- and second-order accurate finite volume schemes are proposed for a general class of hydrodynamic systems with linear and nonlinear damping. The variation of the natural Liapunov functional of the system, given by its free energy, allows, for a characterization of the stationary states by its variation. An analog property at the discrete level enables us to preserve stationary states at machine precision while keeping the dissipation of the discrete free energy. These schemes can accurately analyse the stability properties of stationary states in challenging problems such as: phase transitions in collective behavior, generalized Euler-Poisson systems in chemotaxis and astrophysics, and models in dynamic density functional theories; having done a careful validation in a battery of relevant test cases.

Karakasidis T, Kalliadasis S, Koumoutsakos P,
et al., 2019, Preface, *Computational Materials Science*, Vol: 169, Pages: 109096-109096, ISSN: 0927-0256

Thompson AB, Gomes SN, Denner F,
et al., 2019, Robust low-dimensional modelling of falling liquid films subject to variable wall heating, *Journal of Fluid Mechanics*, Vol: 877, Pages: 844-881, ISSN: 0022-1120

Accurate low-dimensional models for the dynamics of falling liquid films subject to localized or time-varying heating are essential for applications that involve patterning or control. However, existing modelling methodologies either fail to respect fundamental thermodynamic properties or else do not accurately capture the effects of advection and diffusion on the temperature profile. We argue that the best-performing long-wave models are those that give the surface temperature implicitly as the solution of an evolution equation in which the wall temperature alone (and none of its derivatives) appears as a source term. We show that, for both flat and non-uniform films, such a model can be rationally derived by expanding the temperature field about its free-surface values. We test this model in linear and nonlinear regimes, and show that its predictions are in remarkable quantitative agreement with full Navier–Stokes calculations regarding the surface temperature, the internal temperature field and the surface displacement that would result from temperature-induced Marangoni stresses.

Radhakrishnan ANP, Pradas M, Sorensen E,
et al., 2019, Hydrodynamic characterization of phase separation in devices with microfabricated capillaries, *Langmuir*, Vol: 35, Pages: 8199-8209, ISSN: 0743-7463

Capillary microseparators have been gaining interest in downstream unit operations, especially for pharmaceutical, space, and nuclear applications, offering efficient separation of two-phase flows. In this work, a detailed analysis of the dynamics of gas-liquid separation at the single meniscus level helped to formulate a model to map the operability region of microseparation devices. A water-nitrogen segmented flow was separated in a microfabricated silicon-glass device, with a main channel (width, W = 600 μm; height, H = 120 μm) leading into an array of 276 capillaries (100 μm long; width = 5 μm facing the main channel and 25 μm facing the liquid outlet), on both sides of the channel. At optimal pressure differences, the wetting phase (water) flowed through the capillaries into the liquid outlet, whereas the nonwetting phase (nitrogen) flowed past the capillaries into the gas outlet. A high-speed imaging methodology aided by computational analysis was used to quantify the length of the liquid slugs and their positions in the separation zone. It was observed that during stable separation, the position of the leading edge of the liquid slugs (advancing meniscus), which became stationary in the separation zone, was dependent only on the outlet pressure difference. The trailing edge of the liquid slugs (receding meniscus) approached the advancing meniscus at a constant speed, thus leading to a linear decrease of the liquid slug length. Close to the liquid-to-gas breakthrough point, that is, when water exited through the gas outlet, the advancing meniscus was no longer stationary, and the slug lengths decreased exponentially. The rates of decrease of the liquid slug length during separation were accurately estimated by the model, and the calculated liquid-to-gas breakthrough pressures agreed with experimental measurements.

Russo A, Durán-Olivencia MA, Kalliadasis S,
et al., 2019, Macroscopic relations for microscopic properties at the interface between solid substrates and dense fluids, *Journal of Chemical Physics*, Vol: 150, ISSN: 0021-9606

Strongly confined fluids exhibit inhomogeneous properties due to atomistic structuring in close proximity to a solid surface. State variables and transport coefficients at a solid-fluid interface vary locally and become dependent on the properties of the confining walls. However, the precise mechanisms for these effects are not known as of yet. Here, we make use of nonequilibrium molecular dynamics simulations to scrutinize the local fluid properties at the solid-fluid interface for a range of surface conditions and temperatures. We also derive microscopic relations connecting fluid viscosity and density profiles for dense fluids. Moreover, we propose empirical ready-to-use relations to express the average density and viscosity in the channel as a function of temperature, wall interaction strength, and bulk density or viscosity. Such relations are key to technological applications such as micro-/nanofluidics and tribology but also natural phenomena.

Hatipogullari M, Wylock C, Pradas M,
et al., 2019, Contact angle hysteresis in a microchannel: Statics, *Physical Review Fluids*, Vol: 4, ISSN: 2469-990X

We study contact angle hysteresis in a chemically heterogeneous microchannel by tracking static meniscus configurations in the microchannel upon varying the volume of liquid. We first construct a graphical force balance similar to a previous approach by Joanny and de Gennes for this system, though here with a straight contact line. It is shown that hysteresis is induced by wettability gradients above a finite threshold value. This is also visualized in a phase-plane plot enabling to easily predict stick-slip events of the contact line and the occurrence of hysteresis. Above the threshold and for nonoverlapping Gaussian defects, we find good agreement with the expressions by Joanny and de Gennes for the hysteresis amplitude induced by a dilute system of defects. In particular, the hysteresis amplitude is found to be proportional to the square of the defect force and to the defect concentration. For a model sinusoidal heterogeneity, decreasing the ratio between the heterogeneity wavelength and the microchannel gap size brings the system from a subthreshold regime, to a stick-slip dominated regime, and finally to a regime with a quasiconstant advancing and receding angle. In the latter case, the hysteresis amplitude is found to be proportional to the defect force. We also consider an unusual heterogeneity for which the gradients of increasing and decreasing wettability are different. In such a situation breaking the left/right symmetry, whether or not hysteresis is observed will depend on the side the liquid enters the microchannel.

Aymard B, Vaes U, Pradas M,
et al., 2019, A linear, second-order, energy stable, fully adaptive finite element method for phase-field modelling of wetting phenomena, *Journal of Computational Physics: X*, Vol: 2, ISSN: 2590-0552

We propose a new numerical method to solve the Cahn-Hilliard equation coupled with non-linear wetting boundary conditions. We show that the method is mass-conservative and that the discrete solution satisfies a discrete energy law similar to the one satisfied by the exact solution. We perform several tests inspired by realistic situations to verify the accuracy and performance of the method: wetting of a chemically heterogeneous substrate in three dimensions, wetting-driven nucleation in a complex two-dimensional domain and three-dimensional diffusion through a porous medium.

Gomes SN, Kalliadasis S, Pavliotis GA,
et al., 2019, Dynamics of the Desai-Zwanzig model in multiwell and random energy landscapes, *Physical Review E*, Vol: 99, ISSN: 2470-0045

We analyze a variant of the Desai-Zwanzig model [J. Stat. Phys. 19, 1 (1978)]. In particular, we study stationary states of the mean field limit for a system of weakly interacting diffusions moving in a multiwell potential energy landscape, coupled via a Curie-Weiss type (quadratic) interaction potential. The location and depth of the local minima of the potential are either deterministic or random. We characterize the structure and nature of bifurcations and phase transitions for this system, by means of extensive numerical simulations and of analytical calculations for an explicitly solvable model. Our numerical experiments are based on Monte Carlo simulations, the numerical solution of the time-dependent nonlinear Fokker-Planck (McKean-Vlasov) equation, the minimization of the free-energy functional, and a continuation algorithm for the stationary solutions.

Durán-Olivencia MA, Gvalani RS, Kalliadasis S,
et al., 2019, Instability, rupture and fluctuations in thin liquid films: Theory and computations, *Journal of Statistical Physics*, Vol: 174, Pages: 579-604, ISSN: 0022-4715

Thin liquid films are ubiquitous in natural phenomena and technological applications. They have been extensively studied via deterministic hydrodynamic equations, but thermal fluctuations often play a crucial role that needs to be understood. An example of this is dewetting, which involves the rupture of a thin liquid film and the formation of droplets. Such a process is thermally activated and requires fluctuations to be taken into account self-consistently. In this work we present an analytical and numerical study of a stochastic thin-film equation derived from first principles. Following a brief review of the derivation, we scrutinise the behaviour of the equation in the limit of perfectly correlated noise along the wall-normal direction, as opposed to the perfectly uncorrelated limit studied by Grün et al. (J Stat Phys 122(6):1261–1291, 2006). We also present a numerical scheme based on a spectral collocation method, which is then utilised to simulate the stochastic thin-film equation. This scheme seems to be very convenient for numerical studies of the stochastic thin-film equation, since it makes it easier to select the frequency modes of the noise (following the spirit of the long-wave approximation). With our numerical scheme we explore the fluctuating dynamics of the thin film and the behaviour of its free energy in the vicinity of rupture. Finally, we study the effect of the noise intensity on the rupture time, using a large number of sample paths as compared to previous studies.

Savva N, Groves D, Kalliadasis S, 2019, Droplet dynamics on chemically heterogeneous substrates, *Journal of Fluid Mechanics*, Vol: 859, Pages: 321-361, ISSN: 0022-1120

Slow droplet motion on chemically heterogeneous substrates is considered analytically and numerically. We adopt the long-wave approximation which yields a single partial differential equation for the droplet height in time and space. A matched asymptotic analysis in the limit of nearly circular contact lines and vanishingly small slip lengths yields a reduced model consisting of a set of ordinary differential equations for the evolution of the Fourier harmonics of the contact line. The analytical predictions are found, within the domain of their validity, to be in good agreement with the solutions to the governing partial differential equation. The limitations of the reduced model when the contact line undergoes stronger deformations are partially lifted by proposing a hybrid scheme which couples the results of the asymptotic analysis with the boundary integral method. This approach improves the agreement with the governing partial differential equation, but at a computational cost which is significantly lower compared to that required for the full problem.

Schmuck M, Pavliotis GA, Kalliadasis S, 2019, Recent advances in the evolution of interfaces: Thermodynamics, upscaling, and universality, *Computational Materials Science*, Vol: 156, Pages: 441-451, ISSN: 0927-0256

We consider the evolution of interfaces in binary mixtures permeating strongly heterogeneous systems such as porous media. To this end, we first review available thermodynamic formulations for binary mixtures based on general reversible-irreversible couplings and the associated mathematical attempts to formulate a non-equilibrium variational principle in which these non-equilibrium couplings can be identified as minimizers. Based on this, we investigate two microscopic binary mixture formulations fully resolving heterogeneous/perforated domains: (a) a flux-driven immiscible fluid formulation without fluid flow; (b) a momentum-driven formulation for quasi-static and incompressible velocity fields. In both cases we state two novel, reliably upscaled equations for binary mixtures/multiphase fluids in strongly heterogeneous systems by systematically taking thermodynamic features such as free energies into account as well as the system's heterogeneity defined on the microscale such as geometry and materials (e.g. wetting properties). In the context of (a), we unravel a universality with respect to the coarsening rate due to its independence of the system's heterogeneity, i.e. the well-known O(t1/3)-behaviour for homogeneous systems holds also for perforated domains. Finally, the versatility of phase field equations and their thermodynamic foundation relying on free energies, make the collected recent developments here highly promising for scientific, engineering and industrial applications for which we provide an example for lithium batteries.

Lin T-S, Tseluiko D, Blyth MG,
et al., 2018, Continuation methods for time-periodic travelling-wave solutions to evolution equations, *Applied Mathematics Letters*, Vol: 86, Pages: 291-297, ISSN: 0893-9659

A numerical continuation method is developed to follow time-periodic travelling-wave solutions of both local and non-local evolution partial differential equations (PDEs). It is found that the equation for the speed of the moving coordinate can be derived naturally from the governing equations together with a condition that breaks the translational symmetry. The derived system of equations allows one to follow the branch of travelling-wave solutions as well as solutions that are time-periodic in a frame of reference travelling at a constant speed. Finally, we show as an example the bifurcation and stability analysis of single and double-pulse waves in long-wave models of electrified falling films.

Blyth MG, Tseluiko D, Lin T-S,
et al., 2018, Two-dimensional pulse dynamics and the formation of bound states on electrified falling films, *Journal of Fluid Mechanics*, Vol: 855, Pages: 210-235, ISSN: 0022-1120

The flow of an electrified liquid film down an inclined plane wall is investigated with the focus on coherent structures in the form of travelling waves on the film surface, in particular, single-hump solitary pulses and their interactions. The flow structures are analysed first using a long-wave model, which is valid in the presence of weak inertia, and second using the Stokes equations. For obtuse angles, gravity is destabilising and solitary pulses exist even in the absence of an electric field. For acute angles, spatially non-uniform solutions exist only beyond a critical value of the electric field strength; moreover, solitary-pulse solutions are present only at sufficiently high supercritical electric-field strengths. The electric field increases the amplitude of the pulses, can generate recirculation zones in the humps and alters the far-field decay of the pulse tails from exponential to algebraic with a significant impact on pulse interactions. A weak-interaction theory predicts an infinite sequence of bound-state solutions for non-electrified flow, and a finite set for electrified flow. The existence of single-hump pulse solutions and two-pulse bound states is confirmed for the Stokes equations via boundary-element computations. In addition, the electric field is shown to trigger a switch from absolute to convective instability, thereby regularising the dynamics, and this is confirmed by time-dependent simulations of the long-wave model.

Charogiannis A, Denner F, Van Wachem B,
et al., 2018, Experimental investigations of liquid falling films flowing under an inclined planar substrate, *Physical Review Fluids*, Vol: 3, ISSN: 2469-990X

We report on detailed and systematic experiments of thin liquid films flowing as a result of the action of gravity under an inverted planar substrate. A measurement technique based on planar laser-induced fluorescence (PLIF) was developed and applied to a range of such flows in order to provide detailed space- and time-resolved film-height information. Specifically, the experimental campaign spanned three inclination angles (β=−15∘, −30∘, and −45∘, in all cases negative with respect to the vertical), two water-glycerol solutions (with Kapitza numbers of Ka=13.1 and 330), and flow Reynolds numbers covering the range Re=0.6–193. The collection optics were arranged so as to interrogate a spanwise section of the flow extending about 40mm symmetrically on either side the centerline of the film span (80mm in total), at a distance 330 mm downstream of the flow inlet. A range of flow regimes, typically characterized by strong three dimensionality and pronounced rivulet formation, were observed depending on the imposed inlet flow conditions. In the lower liquid Kapitza number Ka(=13.1) flows and depending on the flow Re, the free surface of the film was populated by smooth rivulets or regular sequences of solitary pulses that traveled over the rivulets. In the higher liquid Ka(=330) flows, rivulets were observed typically above Re≈30, depending also on the inclination angle, and grew in amplitude until quasi-two-dimensional fronts developed intermittently that were associated with distinct thin-film regions of varying length and frequency. These regions are of particular interest as they are expected to affect strongly the heat and mass transfer capabilities of these flows. The occurrence of the fronts was more pronounced, with higher wave frequencies, in film flows at smaller negative inclinations for the same flow Re. The rivulet amplitude was found to increase at larger inclinations for the same Re and showed a nonmonotonic trend with in

Duran-Olivencia M, Yatsyshin P, Kalliadasis S,
et al., 2018, General framework for nonclassical nucleation, *New Journal of Physics*, Vol: 20, ISSN: 1367-2630

A great deal of experimental evidence suggests that a wide spectrum of phase transitions occur in a multistage manner via the appearance and subsequent transformation of intermediate metastable states. Such multistage mechanisms cannot be explained within the realm of the classical nucleation framework. Hence, there is a strong need to develop new theoretical tools to explain the occurrence and nature of these ubiquitous intermediate phases. Here we outline a unified and self-consistent theoretical framework to describe both classical and nonclassical nucleation. Our framework provides a detailed explanation of the whole multistage nucleation pathway showing in particular that the pathway involves a single energy barrier and it passes through a dense phase, starting from a low-density initial phase, before reaching the final stable state. Moreover, we demonstrate that the kinetics of matter inside subcritical clusters favors the formation of nucleation clusters with an intermediate density, i.e. nucleation precursors. Remarkably, these nucleation precursors are not associated with a local minimum of the thermodynamic potential, as commonly assumed in previous phenomenological approaches. On the contrary, we find that they emerge due to the competition between thermodynamics and kinetics of cluster formation. Thus, the mechanism uncovered for the formation of intermediate phases can be used to explain recently reported experimental findings in crystallization: up to now such phases were assumed a consequence of some complex energy landscape with multiple energy minima. Using fundamental concepts from kinetics and thermodynamics, we provide a satisfactory explanation for the so-called nonclassical nucleation pathways observed in experiments.

Braga C, Smith E, Nold A,
et al., 2018, The pressure tensor across a liquid-vapour interface, *Journal of Chemical Physics*, Vol: 149, ISSN: 0021-9606

Inhomogeneous fluids exhibit physical properties that are neither uniform nor isotropic. The pressure tensor is a case in point, key to the mechanical description of the interfacial region. Kirkwood and Buff and, later, Irving and Kirkwood, obtained a formal treatment based on the analysis of the pressure across a planar surface [J. G. Kirkwood and F. P. Buff, J. Chem. Phys. 17(3), 338 (1949); J. H. Irving and J. G. Kirkwood, J. Chem. Phys. 18, 817 (1950)]. We propose a generalisation of Irving and Kirkwood’s argument to fluctuating, non-planar surfaces and obtain an expression for the pressure tensor that is not smeared by thermal fluctuations at the molecular scale and corresponding capillary waves [F. P. Buff et al., Phys. Rev. Lett. 15, 621–623 (1965)]. We observe the emergence of surface tension, defined as an excess tangential stress, acting exactly across the dividing surface at the sharpest molecular resolution. The new statistical mechanical expressions extend current treatments to fluctuating inhomogeneous systems far from equilibrium.

Yatsyshin P, Duran-Olivencia MA, Kalliadasis S, 2018, Microscopic aspects of wetting using classical density-functional theory., *Journal of Physics: Condensed Matter*, Vol: 30, ISSN: 0953-8984

Wetting is a rather efficient mechanism for nucleation of a phase (typically liquid) on the interface between two other phases (typically solid and gas). In many experimentally accessible cases of wetting, the interplay between the substrate structure, and the fluid-fluid and fluid-substrate intermolecular interactions brings about an entire ``zoo" of possible fluid configurations, such as liquid films with a thickness of a few nanometers, liquid nanodrops and liquid bridges. These fluid configurations are often associated with phase transitions occurring at the solid-gas interface and at lengths of just several molecular diameters away from the substrate. In this special issue article, we demonstrate how a fully microscopic classical density-functional framework can be applied to the efficient, rational and systematic exploration of the rich phase space of wetting phenomena. We consider a number of model prototype systems such as wetting on a planar wall, a chemically patterned wall and a wedge. Through density-functional computations we demonstrate that for these simply structured substrates the behaviour of the solid-gas interface is already highly complex and non-trivial.

Yatsyshin P, Kalliadasis S, 2018, Classical density-functional theory studies of fluid adsorption on nanopatterned planar surfaces, Workshop on Coupled Mathematical Models for Physical and Nanoscale Systems and their Applications, Publisher: Springer, Pages: 171-185

This contribution is based on our talk at the BIRS Workshop on “Coupled Mathematical Models for Physical and Biological Nanoscale Systems and Their Applications”. Our aim here is to summarize and bring together recent advances in wetting of nanostructured surfaces, using classical density-functional theory (DFT). Classical DFT is an ab initio theoretical-computational framework with a firm foundation in statistical physics allowing us to systematically account for the fluid spatial inhomogeneity, as well as for the non-localities of intermolecular fluid-fluid and fluid-substrate interactions. The cornerstone of classical DFT, is to express the grand free energy of the system as a functional of its one-body density, thus generating a hierarchy of N-body correlation functions. Unconstrained minimization of a properly approximated free-energy functional with respect to the one-body density then yields the basic DFT equation. And since most macroscopic quantities of interest can often be cast as averages over a one-body distribution, this equation provides a very useful and accessible computational tool. Indeed, there has been a rapid growth of classical DFT applications across a broad variety of fields, including phase transitions in solutions of macromolecules, interfacial phenomena, and even nucleation. Here we attempt to give a taste of what simple equilibrium DFT models look like, and what they can and cannot capture, as far as wetting on chemically heterogeneous substrates is concerned. We review recent progress in the understanding of planar prewetting and interface unbending on such substrates and compute substrate-fluid interfaces and wetting isotherms.

Radhakrishnan ANP, Pradas M, Kalliadasis S, et al., 2018, Nonlinear dynamics of gas-liquid separation in a capillary microseparator, ASME 2018 16th International Conference on Nanochannels, Microchannels, and Minichannels (ICNMM2018), Publisher: ASME, Pages: ICNMM2018-7613-ICNMM2018-7613

Copyright © 2018 ASME. Micro-engineered devices (MED) are seeing a significant growth in performing separation processes1. Such devices have been implemented in a range of applications from chemical catalytic reactors to product purification systems like microdistillation. One of the biggest advantages of these devices is the dominance of capillarity and interfacial tension forces. A field where MEDs have been used is in gas-liquid separations. These are encountered, for example, after a chemical reactor, where a gaseous component being produced needs immediate removal from the reactor, because it can affect subsequent reactions. The gaseous phase can be effectively removed using an MED with an array of microcapillaries. Phase-separation can then be brought about in a controlled manner along these capillary structures. For a device made from a hydrophilic material (e.g. Si or glass), the wetted phase (e.g. water) flows through the capillaries, while the non-wetted dispersed phase (e.g. gas) is prevented from entering the capillaries, due to capillary pressure. Separation of liquid-liquid flows can also be achieved via this approach. However, the underlying mechanism of phase separation is far from being fully understood. The pressure at which the gas phase enters the capillaries (gas-to-liquid breakthrough) can be estimated from the Young-Laplace equation, governed by the surface tension (γ) of the wetted phase, capillary width (d) and height (h), and the interface equilibrium contact angle (θeq). Similarly, the liquid-to-gas breakthrough pressure (i.e. the point at which complete liquid separation ceases and liquid exits through the gas outlet) can be estimated from the pressure drop across the capillaries via the Hagen-Poiseuille (HP) equation. Several groups reported deviations from these estimates and therefore, included various parameters to account for the deviations. These parameters usually account for (i) flow of wetted phase through 'n' ca

Yatsyshin P, Parry AO, Rascon C,
et al., 2018, Wetting of a plane with a narrow solvophobic stripe, *Molecular Physics*, Vol: 116, Pages: 1990-1997, ISSN: 0026-8976

We present a numerical study of a simple density functional theory model of fluidadsorption occurring on a planar wall decorated with a narrow deep stripe of aweaker adsorbing (relatively solvophobic) material, where wall-fluid and fluid-fluidintermolecular forces are considered to be dispersive. Both the stripe and outersubstrate exhibit first-order wetting transitions with the wetting temperature ofthe stripe lying above that of the outer material. This geometry leads to a richphase diagram due to the interplay between the pre-wetting transition of the outersubstrate and an unbending transition corresponding to the local evaporation ofliquid near the stripe. Depending on the width of the stripe the line of unbendingtransitions merges with the pre-wetting line inducing a two-dimensional wettingtransition occurring across the substrate. In turn, this leads to the continuous pre-drying of the thick pre-wetting film as the pre-wetting line is approached from above.Interestingly we find that the merging of the unbending and pre-wetting lines occurseven for the widest stripes considered. This contrasts markedly with the scenariowhere the outer material has the higher wetting temperature, for which the mergingof the unbending and pre-wetting lines only occurs for very narrow stripes.

Nold A, González MacDowell L, Sibley DN,
et al., 2018, The vicinity of an equilibrium three-phase contact line using density-functional theory: density profiles normal to the fluid interface, *Molecular Physics*, Vol: 116, Pages: 2239-2243, ISSN: 0026-8976

The paper by Nold et al. [Phys. Fluids 26 (7), 072001 (2014)] examined density profiles and the micro-scale structure of an equilibrium three-phase (liquid–vapour–solid) contact line in the immediate vicinity of the wall using elements from the statistical mechanics of classical fluids, namely density-functional theory. The present research note, building on the above work, further contributes to our understanding of the nanoscale structure of a contact line by quantifying the strong dependence of the liquid–vapour density profile on the normal distance to the interface, when compared to the dependence on the vertical distance to the substrate. A recent study by Benet et al. [J. Phys. Chem. C 118 (38), 22079 (2014)] has shown that this could explain the emergence of a film-height-dependent surface tension close to the wall, with implications for the Frumkin–Derjaguin theory.

Ravipati S, Aymard B, Kalliadasis S,
et al., 2018, On the equilibrium contact angle of sessile liquid drops from molecular dynamics, *Journal of Chemical Physics*, Vol: 148, ISSN: 0021-9606

We present a new methodology to estimate the contact angles of sessile drops from molec-ular simulations, by using the Gaussian convolution method of Willard and Chandler (J.Phys. Chem. B, Vol. 114, 1954-1958, 2010) to calculate the coarse-grained density fromatomic coordinates. The iso-density contour with average coarse-grained density valueequal to half of the bulk liquid density is identified as the average liquid-vapor (LV) inter-face. Angles between the unit normal vectors to the average LV interface and unit normalvector to the solid surface, as a function of the distance normal to the solid surface, arecalculated. The cosines of these angles are extrapolated to the three-phase contact line toestimate the sessile drop contact angle. The proposed methodology, which is relativelyeasy to implement, is systematically applied to three systems: (i) a Lennard-Jones (LJ)drop on a featureless LJ9-3surface; (ii) an SPC/E water drop on a featureless LJ9-3sur-face; and (iii) an SPC/E water drop on a graphite surface. The sessile drop contact anglesestimated with our methodology for the first two systems, are shown to be in good agree-ment with the angles predicted from Young’s equation. The interfacial tensions requiredfor this equation are computed by employing the test-area perturbation method for the cor-responding planar interfaces. Our findings suggest that the widely adopted spherical-capapproximation should be used with caution, as it could take a long time for a sessile dropto relax to a spherical shape, of the order of100ns, especially for water molecules initiatedin a lattice configuration on a solid surface. But even though a water drop can take a longtime to reach the spherical shape, we find that the contact angle is well established muchfaster and the drop evolves towards the spherical shape following a constant-contact-anglerelaxation dynamics. Making use of this observation, our methodology allows a good es-timation of the sessile drop

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