470 research outputs found
Orthorhombic Phase of Crystalline Polyethylene: A Constant Pressure Path Integral Monte Carlo Study
In this paper we present a Path Integral Monte Carlo (PIMC) simulation of the
orthorhombic phase of crystalline polyethylene, using an explicit atom force
field with unconstrained bond lengths and angles. This work represents a
quantum extension of our recent classical simulation (J. Chem. Phys. 106, 8918
(1997)). It is aimed both at exploring the applicability of the PIMC method on
such polymer crystal systems, as well as on a detailed assessment of the
importance of quantum effects on different quantities. We used the
ensemble and simulated the system at zero pressure in the temperature range 25
- 300 K, using Trotter numbers between 12 and 144. In order to investigate
finite-size effects, we used chains of two different lengths, C_12 and C_24,
corresponding to the total number of atoms in the super-cell being 432 and 864,
respectively. We show here the results for structural parameters, like the
orthorhombic lattice constants a,b,c, and also fluctuations of internal
parameters of the chains, such as bond lengths and bond and torsional angles.
We have also determined the internal energy and diagonal elastic constants
c_11, c_22 and c_33. We discuss the temperature dependence of the measured
quantities and compare to that obtained from the classical simulation. For some
quantities, we discuss the way they are related to the torsional angle
fluctuation. In case of the lattice parameters we compare our results to those
obtained from other theoretical approaches as well as to some available
experimental data. In order to study isotope effects, we simulated also a
deuterated polyethylene crystal at a low temperature. We also suggest possible
ways of extending this study and present some general considerations concerning
modeling of polymer crystals.Comment: 18 pages, RevTex, 18 figures, 3 tables, submitted to Phys. Rev.
Crossover between Equilibrium and Shear-controlled Dynamics in Sheared Liquids
We present a numerical simulation study of a simple monatomic Lennard-Jones
liquid under shear flow, as a function of both temperature and shear rate. By
investigating different observables we find that i) It exists a line in the
(temperature-shear) plane that sharply marks the boarder between an
``equilibrium'' and a ``shear-controlled'' region for both the dynamic and the
thermodynamic quantities; and ii) Along this line the structural relaxation
time, is proportional to the inverse shear rate, i.e. to the typical time-scale
introduced by the shear flow. Above the line the liquid dynamics is unaffected
by the shear flow, while below it both temperature and shear rate control the
particle motion.Comment: 14 pages, 5 figure
Locally Preferred Structure and Frustration in Glassforming Liquids: A Clue to Polyamorphism?
We propose that the concept of liquids characterized by a given locally
preferred structure (LPS) could help in understanding the observed phenomenon
of polyamorphism. ``True polyamorphism'' would involve the competition between
two (or more) distinct LPS, one favored at low pressure because of its low
energy and one favored at high pressure because of its small specific volume,
as in tetrahedrally coordinated systems. ``Apparent polyamorphism'' could be
associated with the existence of a poorly crystallized defect-ordered phase
with a large unit cell and small crystallites, which may be illustrated by the
metastable glacial phase of the fragile glassformer triphenylphosphite; the
apparent polyamorphism might result from structural frustration, i. e., a
competition between the tendency to extend the LPS and a global constraint that
prevents tiling of the whole space by the LPS.Comment: 11, 6 figures, Proceedings of the Conference "Horizons in Complex
Systems", Messina; in honor of the 60th birthday of H.E. Stanle
Molecular structural order and anomalies in liquid silica
The present investigation examines the relationship between structural order,
diffusivity anomalies, and density anomalies in liquid silica by means of
molecular dynamics simulations. We use previously defined orientational and
translational order parameters to quantify local structural order in atomic
configurations. Extensive simulations are performed at different state points
to measure structural order, diffusivity, and thermodynamic properties. It is
found that silica shares many trends recently reported for water [J. R.
Errington and P. G. Debenedetti, Nature 409, 318 (2001)]. At intermediate
densities, the distribution of local orientational order is bimodal. At fixed
temperature, order parameter extrema occur upon compression: a maximum in
orientational order followed by a minimum in translational order. Unlike water,
however, silica's translational order parameter minimum is broad, and there is
no range of thermodynamic conditions where both parameters are strictly
coupled. Furthermore, the temperature-density regime where both structural
order parameters decrease upon isothermal compression (the structurally
anomalous regime) does not encompass the region of diffusivity anomalies, as
was the case for water.Comment: 30 pages, 8 figure
Shear yielding of amorphous glassy solids: Effect of temperature and strain rate
We study shear yielding and steady state flow of glassy materials with
molecular dynamics simulations of two standard models: amorphous polymers and
bidisperse Lennard-Jones glasses. For a fixed strain rate, the maximum shear
yield stress and the steady state flow stress in simple shear both drop
linearly with increasing temperature. The dependence on strain rate can be
described by a either a logarithm or a power-law added to a constant. In marked
contrast to predictions of traditional thermal activation models, the rate
dependence is nearly independent of temperature. The relation to more recent
models of plastic deformation and glassy rheology is discussed, and the
dynamics of particles and stress in small regions is examined in light of these
findings
A test of non-equilibrium thermodynamics in glassy systems: the soft-sphere case
The scaling properties of the soft-sphere potential allow the derivation of
an exact expression for the pressure of a frozen liquid, i.e., the pressure
corresponding to configurations which are local minima in its multidimensional
potential energy landscape. The existence of such a relation offers the unique
possibility for testing the recently proposed extension of the liquid free
energy to glassy out-of-equilibrium conditions and the associated expression
for the temperature of the configurational degrees of freedom. We demonstrate
that the non-equilibrium free energy provides an exact description of the
soft-sphere pressure in glass states
Electrification of granular systems of identical insulators
Insulating particles can become highly electrified during powder handling,
volcanic eruptions, and the wind-blown transport of dust, sand, and snow.
Measurements in these granular systems have found that smaller particles
generally charge negatively, while larger particles charge positively. These
observations are puzzling, since particles in these systems are generally
chemically identical, and thus have no contact potential difference. We show
here that simple geometry leads to a net transfer of electrons from larger to
smaller particles, in agreement with these observations. We integrate this
charging mechanism into the first quantitative charging scheme for a granular
system of identical insulators, and show that its predictions are in agreement
with measurements. Our theory thus seems to provide an explanation for the
hitherto puzzling phenomenon of the size-dependent charging of granular systems
of identical insulators.Comment: 8 pages, 5 figures, published in Physical Review
Generic mechanism for generating a liquid-liquid phase transition
Recent experimental results indicate that phosphorus, a single-component
system, can have two liquid phases: a high-density liquid (HDL) and a
low-density liquid (LDL) phase. A first-order transition between two liquids of
different densities is consistent with experimental data for a variety of
materials, including single-component systems such as water, silica and carbon.
Molecular dynamics simulations of very specific models for supercooled water,
liquid carbon and supercooled silica, predict a LDL-HDL critical point, but a
coherent and general interpretation of the LDL-HDL transition is lacking. Here
we show that the presence of a LDL and a HDL can be directly related to an
interaction potential with an attractive part and two characteristic
short-range repulsive distances. This kind of interaction is common to other
single-component materials in the liquid state (in particular liquid metals),
and such potentials are often used to decribe systems that exhibit a density
anomaly. However, our results show that the LDL and HDL phases can occur in
systems with no density anomaly. Our results therefore present an experimental
challenge to uncover a liquid-liquid transition in systems like liquid metals,
regardless of the presence of the density anomaly.Comment: 5 pages, 3 ps Fig
Use of the Generalized Gradient Approximation in Pseudopotential Calculations of Solids
We present a study of the equilibrium properties of -bonded solids within
the pseudopotential approach, employing recently proposed generalized gradient
approximation (GGA) exchange correlation functionals. We analyze the effects of
the gradient corrections on the behavior of the pseudopotentials and discuss
possible approaches for constructing pseudopotentials self-consistently in the
context of gradient corrected functionals. The calculated equilibrium
properties of solids using the GGA functionals are compared to the ones
obtained through the local density approximation (LDA) and to experimental
data. A significant improvement over the LDA results is achieved with the use
of the GGA functionals for cohesive energies. For the lattice constant, the
same accuracy as in LDA can be obtained when the nonlinear coupling between
core and valence electrons introduced by the exchange correlation functionals
is properly taken into account. However, GGA functionals give bulk moduli that
are too small compared to experiment.Comment: 15 pages, latex, no figure
Density-functional embedding using a plane-wave basis
The constrained electron density method of embedding a Kohn-Sham system in a
substrate system (first described by P. Cortona, Phys. Rev. B {\bf 44}, 8454
(1991) and T.A. Wesolowski and A. Warshel, J. Phys. Chem {\bf 97}, 8050 (1993))
is applied with a plane-wave basis and both local and non-local
pseudopotentials. This method divides the electron density of the system into
substrate and embedded electron densities, the sum of which is the electron
density of the system of interest. Coupling between the substrate and embedded
systems is achieved via approximate kinetic energy functionals. Bulk aluminium
is examined as a test case for which there is a strong interaction between the
substrate and embedded systems. A number of approximations to the
kinetic-energy functional, both semi-local and non-local, are investigated. It
is found that Kohn-Sham results can be well reproduced using a non-local
kinetic energy functional, with the total energy accurate to better than 0.1 eV
per atom and good agreement between the electron densities.Comment: 11 pages, 4 figure
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