1,180 research outputs found
New Duality Relations for Classical Ground States
We derive new duality relations that link the energy of configurations
associated with a class of soft pair potentials to the corresponding energy of
the dual (Fourier-transformed) potential. We apply them by showing how
information about the classical ground states of short-ranged potentials can be
used to draw new conclusions about the nature of the ground states of
long-ranged potentials and vice versa. They also lead to bounds on the T=0
system energies in density intervals of phase coexistence, the identification
of a one-dimensional system that exhibits an infinite number of ``phase
transitions," and a conjecture regarding the ground states of purely repulsive
monotonic potentials.Comment: 11 pages, 2 figures. Slightly revised version that corrects typos.
This article will be appearing in Physical Review Letters in a slightly
shortened for
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
Potential energy landscape-based extended van der Waals equation
The inherent structures ({\it IS}) are the local minima of the potential
energy surface or landscape, , of an {\it N} atom system.
Stillinger has given an exact {\it IS} formulation of thermodynamics. Here the
implications for the equation of state are investigated. It is shown that the
van der Waals ({\it vdW}) equation, with density-dependent and
coefficients, holds on the high-temperature plateau of the averaged {\it IS}
energy. However, an additional ``landscape'' contribution to the pressure is
found at lower . The resulting extended {\it vdW} equation, unlike the
original, is capable of yielding a water-like density anomaly, flat isotherms
in the coexistence region {\it vs} {\it vdW} loops, and several other desirable
features. The plateau energy, the width of the distribution of {\it IS}, and
the ``top of the landscape'' temperature are simulated over a broad reduced
density range, , in the Lennard-Jones fluid. Fits to the
data yield an explicit equation of state, which is argued to be useful at high
density; it nevertheless reproduces the known values of and at the
critical point
Evaluation of configurational entropy of a model liquid from computer simulations
Computer simulations have been employed in recent years to evaluate the
configurational entropy changes in model glass-forming liquids. We consider two
methods, both of which involve the calculation of the `intra-basin' entropy as
a means for obtaining the configurational entropy. The first method involves
the evaluation of the intra-basin entropy from the vibrational frequencies of
inherent structures, by making a harmonic approximation of the local potential
energy topography. The second method employs simulations that confine the
liquid within a localized region of configuration space by the imposition of
constraints; apart from the choice of the constraints, no further assumptions
are made. We compare the configurational entropies estimated for a model liquid
(binary mixture of particles interacting {\it via} the Lennard-Jones potential)
for a range of temperatures, at fixed density.Comment: 10 pages, 5 figures, Proceedings of "Unifying Concepts in Glass
Physics" Trieste 1999 (to appear in J. Phys. Cond. Mat.
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
Exact Criterion for Determining Clustering vs. Reentrant Melting Behavior for Bounded Interaction Potentials
We examine in full generality the phase behavior of systems whose constituent
particles interact by means of potentials which do not diverge at the origin,
are free of attractive parts and decay fast enough to zero as the interparticle
separation r goes to infinity. By employing a mean field-density functional
theory which is shown to become exact at high temperatures and/or densities, we
establish a criterion which determines whether a given system will freeze at
all temperatures or it will display reentrant melting and an upper freezing
temperature.Comment: 5 pages, 3 figures, submitted to PRL on March 29, 2000 New version:
10 pages, 9 figures, forwarded to PRE on October 16, 200
Inherent-Structure Dynamics and Diffusion in Liquids
The self-diffusion constant D is expressed in terms of transitions among the
local minima of the potential (inherent structure, IS) and their correlations.
The formulae are evaluated and tested against simulation in the supercooled,
unit-density Lennard-Jones liquid. The approximation of uncorrelated
IS-transition (IST) vectors, D_{0}, greatly exceeds D in the upper temperature
range, but merges with simulation at reduced T ~ 0.50. Since uncorrelated IST
are associated with a hopping mechanism, the condition D ~ D_{0} provides a new
way to identify the crossover to hopping. The results suggest that theories of
diffusion in deeply supercooled liquids may be based on weakly correlated IST.Comment: submitted to PR
Hydrophobic interactions: an overview
We present an overview of the recent progress that has been made in
understanding the origin of hydrophobic interactions. We discuss the different
character of the solvation behavior of apolar solutes at small and large length
scales. We emphasize that the crossover in the solvation behavior arises from a
collective effect, which means that implicit solvent models should be used with
care. We then discuss a recently developed explicit solvent model, in which the
solvent is not described at the atomic level, but rather at the level of a
density field. The model is based upon a lattice-gas model, which describes
density fluctuations in the solvent at large length scales, and a Gaussian
model, which describes density fluctuations at smaller length scales. By
integrating out the small length scale field, a Hamiltonian is obtained, which
is a function of the binary, large-length scale field only. This makes it
possible to simulate much larger systems than hitherto possible as demonstrated
by the application of the model to the collapse of an ideal hydrophobic
polymer. The results show that the collapse is dominated by the dynamics of the
solvent, in particular the formation of a vapor bubble of critical size.
Implications of these findings to the understanding of pressure denaturation of
proteins are discussed.Comment: 10 pages, 4 figure
Densest local packing diversity. II. Application to three dimensions
The densest local packings of N three-dimensional identical nonoverlapping
spheres within a radius Rmin(N) of a fixed central sphere of the same size are
obtained for selected values of N up to N = 1054. In the predecessor to this
paper [A.B. Hopkins, F.H. Stillinger and S. Torquato, Phys. Rev. E 81 041305
(2010)], we described our method for finding the putative densest packings of N
spheres in d-dimensional Euclidean space Rd and presented those packings in R2
for values of N up to N = 348. We analyze the properties and characteristics of
the densest local packings in R3 and employ knowledge of the Rmin(N), using
methods applicable in any d, to construct both a realizability condition for
pair correlation functions of sphere packings and an upper bound on the maximal
density of infinite sphere packings. In R3, we find wide variability in the
densest local packings, including a multitude of packing symmetries such as
perfect tetrahedral and imperfect icosahedral symmetry. We compare the densest
local packings of N spheres near a central sphere to minimal-energy
configurations of N+1 points interacting with short-range repulsive and
long-range attractive pair potentials, e.g., 12-6 Lennard-Jones, and find that
they are in general completely different, a result that has possible
implications for nucleation theory. We also compare the densest local packings
to finite subsets of stacking variants of the densest infinite packings in R3
(the Barlow packings) and find that the densest local packings are almost
always most similar, as measured by a similarity metric, to the subsets of
Barlow packings with the smallest number of coordination shells measured about
a single central sphere, e.g., a subset of the FCC Barlow packing. We
additionally observe that the densest local packings are dominated by the
spheres arranged with centers at precisely distance Rmin(N) from the fixed
sphere's center.Comment: 45 pages, 18 figures, 2 table
The Potential Energy Landscape and Mechanisms of Diffusion in Liquids
The mechanism of diffusion in supercooled liquids is investigated from the
potential energy landscape point of view, with emphasis on the crossover from
high- to low-T dynamics. Molecular dynamics simulations with a time dependent
mapping to the associated local mininum or inherent structure (IS) are
performed on unit-density Lennard-Jones (LJ). New dynamical quantities
introduced include r2_{is}(t), the mean-square displacement (MSD) within a
basin of attraction of an IS, R2(t), the MSD of the IS itself, and g_{loc}(t)
the mean waiting time in a cooperative region. At intermediate T, r2_{is}(t)
posesses an interval of linear t-dependence allowing calculation of an
intrabasin diffusion constant D_{is}. Near T_{c} diffusion is intrabasin
dominated with D = D_{is}. Below T_{c} the local waiting time tau_{loc} exceeds
the time, tau_{pl}, needed for the system to explore the basin, indicating the
action of barriers. The distinction between motion among the IS below T_{c} and
saddle, or border dynamics above T_{c} is discussed.Comment: submitted to pr
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