18 research outputs found
Structural anomalies of fluids: Origins in second and higher coordination shells
Compressing or cooling a fluid typically enhances its static interparticle correlations. However, there are notable exceptions. Isothermal compression can reduce the translational order of fluids that exhibit anomalous waterlike trends in their thermodynamic and transport properties, while isochoric cooling (or strengthening of attractive interactions) can have a similar effect on fluids of particles with short-range attractions. Recent simulation studies by Yan [Phys. Rev. E 76, 051201 (2007)] on the former type of system and Krekelberg [J. Chem. Phys. 127, 044502 (2007)] on the latter provide examples where such structural anomalies can be related to specific changes in second and more distant coordination shells of the radial distribution function. Here, we confirm the generality of this microscopic picture through analysis, via molecular simulation and integral equation theory, of coordination shell contributions to the two-body excess entropy for several related model fluids which incorporate different levels of molecular resolution. The results suggest that integral equation theory can be an effective and computationally inexpensive tool for assessing, based on the pair potential alone, whether new model systems are good candidates for exhibiting structural (and hence thermodynamic and transport) anomalies.Chemical Engineerin
Model for the free-volume distributions of equilibrium fluids
We introduce and test via molecular simulation a simple model for predicting
the manner in which interparticle interactions and thermodynamic conditions
impact the single-particle free-volume distributions of equilibrium fluids. The
model suggests a scaling relationship for the density-dependent behavior of the
hard-sphere system. It also predicts how the second virial coefficients of
fluids with short-range attractions affect their free-volume distributions.Comment: 7 pages, 5 figure
Tuning density profiles and mobility of inhomogeneous fluids
Density profiles are the most common measure of inhomogeneous structure in
confined fluids, but their connection to transport coefficients is poorly
understood. We explore via simulation how tuning particle-wall interactions to
flatten or enhance the particle layering of a model confined fluid impacts its
self-diffusivity, viscosity, and entropy. Interestingly, interactions that
eliminate particle layering significantly reduce confined fluid mobility,
whereas those that enhance layering can have the opposite effect. Excess
entropy helps to understand and predict these trends.Comment: 5 pages, 3 figure
Impact of surface roughness on diffusion of confined fluids
Using event-driven molecular dynamics simulations, we quantify how the self
diffusivity of confined hard-sphere fluids depends on the nature of the
confining boundaries. We explore systems with featureless confining boundaries
that treat particle-boundary collisions in different ways and also various
types of physically (i.e., geometrically) rough boundaries. We show that, for
moderately dense fluids, the ratio of the self diffusivity of a rough wall
system to that of an appropriate smooth-wall reference system is a linear
function of the reciprocal wall separation, with the slope depending on the
nature of the roughness. We also discuss some simple practical ways to use this
information to predict confined hard-sphere fluid behavior in different
rough-wall systems
Composition and concentration anomalies for structure and dynamics of Gaussian-core mixtures
We report molecular dynamics simulation results for two-component fluid
mixtures of Gaussian-core particles, focusing on how tracer diffusivities and
static pair correlations depend on temperature, particle concentration, and
composition. At low particle concentrations, these systems behave like simple
atomic mixtures. However, for intermediate concentrations, the single-particle
dynamics of the two species largely decouple, giving rise to the following
anomalous trends. Increasing either the concentration of the fluid (at fixed
composition) or the mole fraction of the larger particles (at fixed particle
concentration) enhances the tracer diffusivity of the larger particles, but
decreases that of the smaller particles. In fact, at sufficiently high particle
concentrations, the larger particles exhibit higher mobility than the smaller
particles. Each of these dynamic behaviors is accompanied by a corresponding
structural trend that characterizes how either concentration or composition
affects the strength of the static pair correlations. Specifically, the dynamic
trends observed here are consistent with a single empirical scaling law that
relates an appropriately normalized tracer diffusivity to its pair-correlation
contribution to the excess entropy.Comment: 5 pages, 4 figure
Anomalous structure and dynamics of the Gaussian-core fluid
It is known that there are thermodynamic states for which the Gaussian-core
(GC) fluid displays anomalous properties such as expansion upon isobaric
cooling (density anomaly) and increased single-particle mobility upon
isothermal compression (self-diffusivity anomaly). We investigate how
temperature and density affect its short-range translational structural order,
as characterized by the two-body excess entropy. We find that there is a wide
range of conditions for which the short-range translational order of the GC
fluid decreases upon isothermal compression (structural order anomaly). The
origin of the structural anomaly is qualitatively similar to that of other
anomalous fluids and is connected to how compression affects static
correlations at different length scales. We find that the self-diffusivity of
the GC fluid obeys a scaling relationship with the two-body excess entropy that
is very similar to the one observed for a variety of simple liquids. One
consequence of this relationship is that the state points for which structural,
self-diffusivity, and density anomalies of the Gaussian-core fluid occur appear
as cascading regions on the temperature-density plane, a phenomenon observed
earlier for models of waterlike fluids. There are, however, key differences
between the anomalies of GC and waterlike fluids, and we discuss how those can
be qualitatively understood by considering the respective interparticle
potentials of these models. Finally, we note that the self-diffusivity of the
Gaussian-core fluid obeys different scaling laws depending on whether the
two-body or total excess entropy is considered. This finding, which deserves
more comprehensive future study, appears to underscore the significance of
higher-body correlations for the behavior of fluids with bounded interactions.Comment: 6 pages, 3 figure
Generalized Rosenfeld scalings for tracer diffusivities in not-so-simple fluids: Mixtures and soft particles
Rosenfeld [Phys. Rev. A 15, 2545 (1977)] noticed that casting transport
coefficients of simple monatomic, equilibrium fluids in specific dimensionless
forms makes them approximately single-valued functions of excess entropy. This
has predictive value because, while the transport coefficients of dense fluids
are difficult to estimate from first principles, excess entropy can often be
accurately predicted from liquid-state theory. Here, we use molecular
simulations to investigate whether Rosenfeld's observation is a special case of
a more general scaling law relating mobility of particles in mixtures to excess
entropy. Specifically, we study tracer diffusivities, static structure, and
thermodynamic properties of a variety of one- and two-component model fluid
systems with either additive or non-additive interactions of the hard-sphere or
Gaussian-core form. The results of the simulations demonstrate that the effects
of mixture concentration and composition, particle-size asymmetry and
additivity, and strength of the interparticle interactions in these fluids are
consistent with an empirical scaling law relating the excess entropy to a new
dimensionless (generalized Rosenfeld) form of tracer diffusivity, which we
introduce here. The dimensionless form of the tracer diffusivity follows from
knowledge of the intermolecular potential and the transport / thermodynamic
behavior of fluids in the dilute limit. The generalized Rosenfeld scaling
requires less information, and provides more accurate predictions, than either
Enskog theory or scalings based on the pair-correlation contribution to the
excess entropy. As we show, however, it also suffers from some limitations,
especially for systems that exhibit significant decoupling of individual
component tracer diffusivities.Comment: 15 pages, 10 figure
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Shear-rate-dependent structural order and viscosity of a fluid with short-range attractions
We study a model short-range attractive fluid under shear. For this system, the strength of interparticle attractions strongly influences the equilibrium structural order. We find that shear monotonically decreases structural order regardless of the strength of the attractions. There is a strong correlation between shear-rate-dependent viscosity and a structural order metric, suggesting a structurally based constitutive equation. This correlation also holds for the Lennard-Jones fluid.Chemical Engineerin