The two-body (pair) contribution to the entropy of two-dimensional Yukawa systems is calculated and analyzed. It is demonstrated that in the vicinity of the fluid-solid (freezing) phase transition the pair entropy exhibits an abrupt jump in a narrow temperature range and this can be used to identify the freezing point. Relations to the full excess entropy and some existing freezing indicators are briefly discussed.
Molecular dynamics simulations and instantaneous normal mode (INM) analysis of a fluid with core-softened pair interactions and water-like liquid-state anomalies are performed to obtain an understanding of the relationship between thermodynamics, transport properties and the poten- tial energy landscape. Rosenfeld-scaling of diffusivities with the thermodynamic excess and pair correlation entropy is demonstrated for this model. The INM spectra are shown to carry infor- mation about the dynamical consequences of the interplay between length scales characteristic of anomalous fluids, such as bim…
This work investigates the link between residual entropy and viscosity based on wide-ranging, highly accurate experimental and simulation data. This link was originally postulated by Rosenfeld in 1977, and it is shown that this scaling results in an approximately monovariate relationship between residual entropy and reduced viscosity for a wide range of molecular fluids (argon, methane, CO2, SF6, refrigerant R-134a (1,1,1,2-tetrafluoroethane), refrigerant R-125 (pentafluoroethane), methanol, and water), and a range of model potentials (hard sphere, inverse power, Lennard-Jones, and Weeks-Chand…
Consider a deformable body immersed in an incompressible fluid that is randomly stirred. Sticking to physical situations in which the body departs only slightly from its spherical shape, we investigate the deformations of the body. The shape is decomposed into spherical harmonic modes. We study the correlations of these modes for a general class of random flows that include the flow due to thermal agitation. Our results are general in the sense that they are applicable to any body that is described solely by the shape of its surface.
We derive a hierarchy of equations which allow a general $n$-body distribution function to be measured by test-particle insertion of between $1$ and $n$ particles, and successfully apply it to measure the pair and three-body distribution functions in a simple fluid. The insertion-based methods overcome the drawbacks of the conventional distance-histogram approach, offering enhanced structural resolution and a more straightforward normalisation. They will be especially useful in characterising the structure of inhomogeneous fluids and investigating closure approximations in liquid state theory.
Consider a deformable body immersed in an incompressible liquid that is randomly stirred. Sticking to physical situations in which the body departs only slightly from its spherical shape, we investigate the motion of the body, calculate its mean squared displacement for a correlation function of general form and consider several usefull families of correlation functions. We also consider, in detail, the case of thermal agitation and the validity of the small deformation approximation.
Computer simulations are used to test whether a recently introduced generalization of Rosenfeld's excess-entropy scaling method for estimating transport coefficients in systems obeying molecular dynamics can be extended to predict long-time diffusivities in fluids of particles undergoing Brownian dynamics in the absence of interparticle hydrodynamic forces. Model fluids with inverse-power-law, Gaussian-core, and Hertzian pair interactions are considered. Within the generalized Rosenfeld scaling method, long-time diffusivities of ultrasoft Gaussian-core and Hertzian particle fluids, which displ…
A simulation technique is described for quantifying the contribution of three-body interactions to the thermodynamical properties of coarse-grained representations of complex fluids. The method is based on comparing the third virial coefficient $B_3$ for a complex fluid with that of an approximate coarse-grained model described by a pair potential. To obtain $B_3$ we introduce a new technique which expresses its value in terms of the measured volume-dependent asymptote of a certain structural function. The strategy is applicable to both Molecular Dynamics and Monte Carlo simulation. Its utilit…
We describe a general simulation scheme for assessing the thermodynamic consequences of neglecting many-body effects in coarse-grained models of complex fluids. The method exploits the fact that the asymptote of a simple-to-measure structural function provides direct estimates of virial coefficients. Comparing the virial coefficients of an atomistically detailed system with those of a coarse-grained version described by pair potentials, permits the role of many-body effects to be quantified. The approach is applied to two models: (i) a size-asymmetrical colloid-polymer mixture, and (ii) a solu…
We present a new method based on the scattering technique to investigate fluctuation-induced forces at a fluid interface. The scattering approach, well suited to the study of many body systems of arbitrary geometries, is augmented to include boundary fluctuations. Using this method, we study the deviation of the total fluctuation-induced interaction from the sum of pairwise energies for three colloidal particles. We consider both frozen and fluctuating colloids and obtain a very good agreement between analytical and numerical results. We find a marked difference in the three body fluctuation-i…
Because active particles break time-reversal symmetry, an active fluid can sustain currents even without an external drive. We show that when a passive body is placed in a fluid of pairwise interacting active particles, it generates long-range currents, corresponding to density and pressure gradients. By using a multipole expansion and a far-field constitutive relation, we show that the leading-order behavior of all three corresponds to a source dipole. Then, when two bodies or more are placed in the active fluid, generic long-range interactions between the bodies occur. We find these to be qu…
The Stokes-Einstein (SE) relation between the self-diffusion and shear viscosity coefficients operates in sufficiently dense liquids not too far from the liquid-solid phase transition. By considering four simple model systems with very different pairwise interaction potentials (Lennard-Jones, Coulomb, Debye-Hückel or screened Coulomb, and the hard sphere limit) we identify where exactly on the respective phase diagrams the SE relation holds. It appears that the reduced excess entropy $s_{\rm ex}$ can be used as a suitable indicator of the validity of the SE relation. In all cases considered th…
