49,432 research outputs found
A fundamental measure theory for the sticky hard sphere fluid
We construct a density functional theory (DFT) for the sticky hard sphere
(SHS) fluid which, like Rosenfeld's fundamental measure theory (FMT) for the
hard sphere fluid [Phys. Rev. Lett. {\bf 63}, 980 (1989)], is based on a set of
weighted densities and an exact result from scaled particle theory (SPT). It is
demonstrated that the excess free energy density of the inhomogeneous SHS fluid
is uniquely defined when (a) it is solely a function of the
weighted densities from Kierlik and Rosinberg's version of FMT [Phys. Rev. A
{\bf 42}, 3382 (1990)], (b) it satisfies the SPT differential equation, and (c)
it yields any given direct correlation function (DCF) from the class of
generalized Percus-Yevick closures introduced by Gazzillo and Giacometti [J.
Chem. Phys. {\bf 120}, 4742 (2004)]. The resulting DFT is shown to be in very
good agreement with simulation data. In particular, this FMT yields the correct
contact value of the density profiles with no adjustable parameters. Rather
than requiring higher order DCFs, such as perturbative DFTs, our SHS FMT
produces them. Interestingly, although equivalent to Kierlik and Rosinberg's
FMT in the case of hard spheres, the set of weighted densities used for
Rosenfeld's original FMT is insufficient for constructing a DFT which yields
the SHS DCF.Comment: 11 pages, 3 figure
Relationship between Local Molecular Field Theory and Density Functional Theory for non-uniform liquids
The Local Molecular Field Theory (LMF) developed by Weeks and co-workers has
proved successful for treating the structure and thermodynamics of a variety of
non-uniform liquids. By reformulating LMF in terms of one-body direct
correlation functions we recast the theory in the framework of classical
Density Functional Theory (DFT). We show that the general LMF equation for the
effective reference potential phi_R follows directly from the standard
mean-field DFT treatment of attractive interatomic forces. Using an accurate
(Fundamental Measures) DFT for the non-uniform hard-sphere reference fluid we
determine phi_R for a hard-core Yukawa liquid adsorbed at a planar hard wall.
In the approach to bulk liquid-gas coexistence we find the effective potentials
exhibit rich structure that can include damped oscillations at large distances
from the wall as well as the repulsive hump near the wall required to generate
the low density 'gas' layer characteristic of complete drying. We argue that it
would be difficult to obtain the same level of detail from other (non DFT
based) implementations of LMF. LMF emphasizes the importance of making an
intelligent division of the interatomic pair potential of the full system into
a reference part and a remainder that can be treated in mean-field
approximation. We investigate different divisions for an exactly solvable one-
dimensional model where the pair potential has a hard-core plus a linear
attractive tail. Results for the structure factor and the equation of state of
the uniform fluid show that including a significant portion of the attraction
in the reference system can be much more accurate than treating the full
attractive tail in mean-field approximation. We discuss further aspects of the
relationship between LMF and DFT.Comment: 35 pages, 10 Fig
On the nonlocal viscosity kernel of mixtures
In this report we investigate the multiscale hydrodynamical response of a
liquid as a function of mixture composition. This is done via a series of
molecular dynamics simulations where the wave vector dependent viscosity kernel
is computed for three mixtures each with 7-15 different compositions. We
observe that the nonlocal viscosity kernel is dependent on composition for
simple atomic mixtures for all the wave vectors studied here, however, for a
model polymer melt mixture the kernel is independent of composition for large
wave vectors. The deviation from ideal mixing is also studied. Here it is shown
that a Lennard-Jones mixture follows the ideal mixing rule surprisingly well
for a large range of wave vectors, whereas for both the Kob-Andersen mixture
and the polymer melt large deviations are found. Furthermore, for the polymer
melt the deviation is wave vector dependent such that there exists a critical
length scale at which the ideal mixing goes from under-estimating to
over-estimating the viscosity
Toward the Jamming Threshold of Sphere Packings: Tunneled Crystals
We have discovered a new family of three-dimensional crystal sphere packings
that are strictly jammed (i.e., mechanically stable) and yet possess an
anomalously low density. This family constitutes an uncountably infinite number
of crystal packings that are subpackings of the densest crystal packings and
are characterized by a high concentration of self-avoiding "tunnels" (chains of
vacancies) that permeate the structures. The fundamental geometric
characteristics of these tunneled crystals command interest in their own right
and are described here in some detail. These include the lattice vectors (that
specify the packing configurations), coordination structure, Voronoi cells, and
density fluctuations. The tunneled crystals are not only candidate structures
for achieving the jamming threshold (lowest-density rigid packing), but may
have substantially broader significance for condensed matter physics and
materials science.Comment: 19 pages, 5 figure
Dynamical density functional theory with hydrodynamic interactions and colloids in unstable traps
A density functional theory for colloidal dynamics is presented which
includes hydrodynamic interactions between the colloidal particles. The theory
is applied to the dynamics of colloidal particles in an optical trap which
switches periodically in time from a stable to unstable confining potential. In
the absence of hydrodynamic interactions, the resulting density breathing mode,
exhibits huge oscillations in the trap center which are almost completely
damped by hydrodynamic interactions. The predicted dynamical density fields are
in good agreement with Brownian dynamics computer simulations
The health state preferences and logistical inconsistencies of New Zealanders: a tale of two tariffs
Notwithstanding the proposed use of Cost-Utility Analysis (CUA) to inform health care priority setting in New Zealand, to date there has been no research into New Zealanders’ valuations of health-related quality of life. This paper reports the results of a study of the health state preferences of adult New Zealanders generated from a postal survey to which 1360 people responded (a 50% response rate). The survey employed a self-completed questionnaire in which a selection of health states were described using the EQ-5D health state classification system and respondents’ valuations were sought using a visual analogue scale (VAS). Close attention is paid to the quality of the data, in particular to the ‘logical inconsistencies’ in respondents’ valuations. Regression analysis is used to interpolate values over the 245 possible EQ-5D states. Two tariffs of health state preferences, arising from contrasting treatments of the logical inconsistencies, are reported.New Zealand, EuroQol, EQ-5D
The standard mean-field treatment of inter-particle attraction in classical DFT is better than one might expect
In classical density functional theory (DFT) the part of the Helmholtz free
energy functional arising from attractive inter-particle interactions is often
treated in a mean-field or van der Waals approximation. On the face of it, this
is a somewhat crude treatment as the resulting functional generates the simple
random phase approximation (RPA) for the bulk fluid pair direct correlation
function. We explain why using standard mean-field DFT to describe
inhomogeneous fluid structure and thermodynamics is more accurate than one
might expect based on this observation. By considering the pair correlation
function and structure factor of a one-dimensional model fluid,
for which exact results are available, we show that the mean-field DFT,
employed within the test-particle procedure, yields results much superior to
those from the RPA closure of the bulk Ornstein-Zernike equation. We argue that
one should not judge the quality of a DFT based solely on the approximation it
generates for the bulk pair direct correlation function.Comment: 9 pages, 3 figure
New Green-Kubo formulas for transport coefficients in hard sphere-, Langevin fluids and the likes
We present generalized Green-Kubo expressions for thermal transport
coefficients in non-conservative fluid-type systems, of the generic form,
+\int^\infty_0 dt V^{-1} \av{I_\epsilon \exp(t {\cal L})
I}_0 where is a pseudo-streaming operator. It consists of a
sum of an instantaneous transport coefficient , and a time integral
over a time correlation function in a state of thermal equilibrium between a
current and its conjugate current . This formula with
and covers vastly different systems,
such as strongly repulsive elastic interactions in hard sphere fluids, weakly
interacting Langevin fluids with dissipative and stochastic interactions
satisfying detailed balance conditions, and "the likes", defined in the text.
For conservative systems the results reduce to the standard formulas.Comment: 7 pages, no figures. Version 2: changes in the text and references
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Nonequilibrium static growing length scales in supercooled liquids on approaching the glass transition
The small wavenumber behavior of the structure factor of
overcompressed amorphous hard-sphere configurations was previously studied for
a wide range of densities up to the maximally random jammed state, which can be
viewed as a prototypical glassy state [A. Hopkins, F. H. Stillinger and S.
Torquato, Phys. Rev. E, 86, 021505 (2012)]. It was found that a precursor to
the glassy jammed state was evident long before the jamming density was reached
as measured by a growing nonequilibrium length scale extracted from the volume
integral of the direct correlation function , which becomes long-ranged
as the critical jammed state is reached. The present study extends that work by
investigating via computer simulations two different atomic models: the
single-component Z2 Dzugutov potential in three dimensions and the
binary-mixture Kob-Andersen potential in two dimensions. Consistent with the
aforementioned hard-sphere study, we demonstrate that for both models a
signature of the glass transition is apparent well before the transition
temperature is reached as measured by the length scale determined from from the
volume integral of the direct correlation function in the single-component case
and a generalized direct correlation function in the binary-mixture case. The
latter quantity is obtained from a generalized Orstein-Zernike integral
equation for a certain decoration of the atomic point configuration. We also
show that these growing length scales, which are a consequence of the
long-range nature of the direct correlation functions, are intrinsically
nonequilibrium in nature as determined by an index that is a measure of
deviation from thermal equilibrium. It is also demonstrated that this
nonequilibrium index, which increases upon supercooling, is correlated with a
characteristic relaxation time scale.Comment: 26 pages, 14 figure
Theoretical Description of Coulomb Balls - Fluid Phase
A theoretical description for the radial density profile of a finite number
of identical charged particles confined in a harmonic trap is developed for
application over a wide range of Coulomb coupling (or, equivalently,
temperatures) and particle numbers. A simple mean field approximation
neglecting correlations yields a density profile which is monotonically
decreasing with radius for all temperatures, in contrast to molecular dynamics
simulations and experiments showing shell structure at lower temperatures. A
more complete theoretical description including charge correlations is
developed here by an extension of the hypernetted chain approximation,
developed for bulk fluids, to the confined charges. The results reproduce all
of the qualitative features observed in molecular dynamics simulations and
experiments. These predictions are then tested quantitatively by comparison
with new benchmark Monte Carlo simulations. Quantitative accuracy of the theory
is obtained for the selected conditions by correcting the hypernetted chain
approximation with a representation for the associated bridge functions.Comment: 10 figures, submitted to Physical Review
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