Andreas Nold

General Dynamical Density Functional Theory for Classical Fluids

We study the dynamics of a colloidal fluid in the full position-momentum phase space. The full underlying model consists of the Langevin equations including hydrodynamic interactions, which strongly influence the non-equilibrium properties of the system. For large systems, the number of degrees of freedom prohibit a direct solution of the Langevin equations and a reduced model is necessary, e.g. a projection of the dynamics to those of the reduced one-body distribution. We derive a generalized dynamical density functional theory (DDFT), the computational complexity of which is independent of the number of particles. We demonstrate that, in suitable limits, we recover existing DDFTs, which neglect either inertia, or hydrodynamic interactions, or both. In particular, in the overdamped limit we obtain a DDFT describing only the position distribution, and with a novel definition of the diffusion tensor. Futhermore, near equilibrium, our DDFT reduces to a Navier-Stokes-like equation but with additional non-local terms. We also demonstrate the very good agreement between the new DDFT and full stochastic calculations, as well as the large qualitative effects of inertia and hydrodynamic interactions.

Unification of dynamic density functional theory for colloidal fluids to include inertia and hydrodynamic interactions: derivation and numerical experiments

Starting from the Kramers equation for the phase-space dynamics of the N-body probability distribution, we derive a dynamical density functional theory (DDFT) for colloidal fluids including the effects of inertia and hydrodynamic interactions (HI). We compare the resulting theory to extensive Langevin dynamics simulations for both hard rod systems and three-dimensional hard sphere systems with radially symmetric external potentials. As well as demonstrating the accuracy of the new DDFT, by comparing with previous DDFTs which neglect inertia, HI, or both, we also scrutinize the significance of including these effects. Close to local equilibrium we derive a continuum equation from the microscopic dynamics which is a generalized Navier-Stokes-like equation with additional non-local terms governing the effects of HI. For the overdamped limit we recover analogues of existing configuration-space DDFTs but with a novel diffusion tensor.

Fluid structure in the immediate vicinity of an equilibrium three-phase contact line and assessment of disjoining pressure models using density functional theory

We examine the nanoscale behavior of an equilibrium three-phase contact line in the presence of long-ranged intermolecular forces by employing a statistical mechanics of fluids approach, namely density functional theory (DFT) together with fundamental measure theory (FMT). This enables us to evaluate the predictive quality of effective Hamiltonian models in the vicinity of the contact line. In particular, we compare the results for mean field effective Hamiltonians with disjoining pressures defined through (I) the adsorption isotherm for a planar liquid film, and (II) the normal force balance at the contact line. We find that the height profile obtained using (I) shows good agreement with the adsorption film thickness of the DFT-FMT equilibrium density profile in terms of maximal curvature and the behavior at large film heights. In contrast, we observe that while the height profile obtained by using (II) satisfies basic sum rules, it shows little agreement with the adsorption film thickness of the DFT results. The results are verified for contact angles of 20, 40 and 60 degrees.

The contact line behaviour of solid-liquid-gas diffuse-interface models

A solid-liquid-gas moving contact line is considered through a diffuse-interface model with the classical boundary condition of no-slip at the solid surface. Examination of the asymptotic behaviour as the contact line is approached shows that the relaxation of the classical model of a sharp liquid-gas interface, whilst retaining the no-slip condition, resolves the stress, and pressure singularities associated with the moving contact line problem while the fluid velocity is well defined (not multi-valued). The moving contact line behaviour is analysed for a general problem relevant for any density dependent dynamic viscosity and volume viscosity, and for general microscopic contact angle and double well free-energy forms. Away from the contact line, analysis of the diffuse-interface model shows that the Navier–Stokes equations and classical interfacial boundary conditions are obtained at leading order in the sharp-interface limit, justifying the creeping flow problem imposed in an intermediate region in the seminal work of Seppecher [Int. J. Eng. Sci. 34, 977–992 (1996)]. Corrections to Seppechers work are given, as an incorrect solution form was originally used.

A comparison of slip, disjoining pressure, and interface formation models for contact line motion through asymptotic analysis of thin two-dimensional droplet spreading

The motion of a contact line is examined, and comparisons drawn, for a variety of models proposed in the literature. Pressure and stress behaviours at the contact line are examined in the prototype system of quasistatic spreading of a thin two-dimensional droplet on a planar substrate. The models analysed include three disjoining pressure models based on van der Waals interactions, a model introduced for polar fluids, and a liquid–gas diffuse-interface model; Navier-slip and two non-linear slip models are investigated, with three microscopic contact angle boundary conditions imposed (two of these contact angle conditions having a contact line velocity dependence); and the interface formation model is also considered. In certain parameter regimes it is shown that all of the models predict the same quasistatic droplet spreading behaviour.

On the moving contact line singularity: Asymptotics of a diffuse-interface model

The behaviour of a solid-liquid-gas system near the three-phase contact line is considered using a diffuse-interface model with no-slip at the solid and where the fluid phase is specified by a continuous density field. Relaxation of the classical approach of a sharp liquid-gas interface and careful examination of the asymptotic behaviour as the contact line is approached is shown to resolve the stress and pressure singularities associated with the moving contact line problem. Various features of the model are scrutinised, alongside extensions to incorporate slip, finite-time relaxation of the chemical potential, or a precursor film at the wall.Graphical abstract

Multi-species dynamical density functional theory

We study the dynamics of a multi-species colloidal fluid in the full position-momentum phase space. We include both inertia and hydrodynamic interactions, which strongly influence the non-equilibrium properties of the system. Under minimal assumptions, we derive a dynamical density functional theory (DDFT), and, using an efficient numerical scheme based on spectral methods for integro-differential equations, demonstrate its excellent agreement with the full underlying Langevin equations. We utilise the DDFT formalism to elucidate the crucial effects of hydrodynamic interactions in multi-species systems.

Nanoscale fluid structure of liquid-solid-vapour contact lines for a wide range of contact angles

We study the nanoscale behaviour of the density of a simple fluid in the vicinity of an equilibrium contact line for a wide range of Young contact angles between 40 and 135 degrees. Cuts of the density profile at various positions along the contact line are presented, unravelling the apparent step-wise increase of the film height profile observed in contour plots of the density. The density profile is employed to compute the normal pressure acting on the substrate along the contact line. We observe that for the full range of contact angles, the maximal normal pressure cannot solely be predicted by the curvature of the adsorption film height, but is instead softened -- likely by the width of the liquid-vapour interface. Somewhat surprisingly however, the adsorption film height profile can be predicted to a very good accuracy by the Derjaguin-Frumkin disjoining pressure obtained from planar computations, as was first shown in [Nold et al., Phys. Fluids, 26, 072001, 2014] for contact angles less than 90 degrees, a result which here we show to be valid for the full range of contact angles. This suggests that while two-dimensional effects cannot be neglected for the computation of the normal pressure distribution along the substrate, one-dimensional planar computations of the Derjaguin-Frumkin disjoining pressure are sufficient to accurately predict the adsorption height profile.

Dynamical Density Functional Theory with Hydrodynamic Interactions in Confined Geometries

We study the dynamics of colloidal fluids in both unconfined geometries and when confined by a hard wall. Under minimal assumptions, we derive a dynamical density functional theory (DDFT) which includes hydrodynamic interactions (HI; bath-mediated forces). By using an efficient numerical scheme based on pseudospectral methods for integro-differential equations, we demonstrate its excellent agreement with the full underlying Langevin equations for systems of hard disks in partial confinement. We further use the derived DDFT formalism to elucidate the crucial effects of HI in confined systems.

Nonequilibrium molecular dynamics simulations of nanoconfined fluids at solid-liquid interfaces

We investigate the hydrodynamic properties of a Lennard-Jones fluid confined to a nanochannel using molecular dynamics simulations. For channels of different widths and hydrophilic-hydrophobic surface wetting properties, profiles of the fluid density, stress, and viscosity across the channel are obtained and analysed. In particular, we propose a linear relationship between the density and viscosity in confined and strongly inhomogeneous nanofluidic flows. The range of validity of this relationship is explored in the context of coarse grained models such as dynamic density functional-theory.