97 research outputs found
Thermodynamic, Dynamic and Structural Anomalies for Shoulder-like potentials
Using molecular dynamic simulations we study a family of continuous
core-softened potentials consisting of a hard core, a shoulder at closest
distances and an attractive well at further distance. The repulsive shoulder
and the well distances represent two length scales. We show that if the first
scale, the shoulder, is repulsive or has a small well, the potential has a
region in the pressure-temperature phase diagram with density, diffusion and
structural anomalies. However, if the closest scale becomes a deep attractive
well the regions in the pressure-temperature phase diagram where the three
anomalies are present shrink and disappear. This result enables us to predict
by the shape of the core-softened potential if anomalies would or would not be
present
Diffusion in simple fluids
Computed self diffusion coefficients for the Lennard-Jones and hard sphere fluids are related by
Dej = DNs(aB) exp (--e/2kB T)
where ÏB=ÏLJ(2/[1+ii(1+2kBT/Δ)])1/6, the effective hard sphere diameter, is the (average) distance of closest approach in collisions between molecules which interact with the positive part of the LJ potential, and the Arrhenius term reflects the influence of the negative part. ÏLJ and Δ are the size and well depth parameters. Measured diffusion coefficients of the halomethane liquids are reproduced by the equation over wide ranges of temperature and density and do not reveal any influence of the inelastic effects associated with molecular anisotropy
Relation Between the Widom line and the Strong-Fragile Dynamic Crossover in Systems with a Liquid-Liquid Phase Transition
We investigate, for two water models displaying a liquid-liquid critical
point, the relation between changes in dynamic and thermodynamic anomalies
arising from the presence of the liquid-liquid critical point. We find a
correlation between the dynamic fragility transition and the locus of specific
heat maxima (``Widom line'') emanating from the critical point.
Our findings are consistent with a possible relation between the previously
hypothesized liquid-liquid phase transition and the transition in the dynamics
recently observed in neutron scattering experiments on confined water. More
generally, we argue that this connection between and dynamic
crossover is not limited to the case of water, a hydrogen bond network forming
liquid, but is a more general feature of crossing the Widom line. Specifically,
we also study the Jagla potential, a spherically-symmetric two-scale potential
known to possess a liquid-liquid critical point, in which the competition
between two liquid structures is generated by repulsive and attractive ramp
interactions.Comment: 6 pages and 5 figure
Diffusion Anomaly in an Associating Lattice Gas Model
We investigate the relation between thermodynamic and dynamic properties of
an associating lattice gas (ALG) model. The ALG combines a two dimensional
lattice gas with particles interacting through a soft core potential and
orientational degrees of freedom. From the competition between the directional
attractive forces and the soft core potential results two liquid phases, double
criticality and density anomaly. We study the mobility of the molecules in this
model by calculating the diffusion constant at a constant temperature, . We
show that has a maximum at a density and a minimum at a
density . Between these densities the diffusivity
differs from the one expected for normal liquids. We also show that in the
pressure-temperature phase-diagram the line of extrema in diffusivity is close
to the liquid-liquid critical point and it is inside the temperature of maximum
density (TMD) line.Comment: 12 pages, 9 figure
Density anomaly in a competing interactions lattice gas model
We study a very simple model of a short-range attraction and an outer shell
repulsion as a test system for demixing phase transition and density anomaly.
The phase-diagram is obtained by applying mean field analysis and Monte Carlo
simulations to a two dimensional lattice gas with nearest-neighbors attraction
and next-nearest-neighbors repulsion (the outer shell). Two liquid phases and
density anomaly are found.
The coexistence line between these two liquid phases meets a critical line
between the fluid and the low density liquid at a tricritical point. The line
of maximum density emerges in the vicinity of the tricritical point, close to
the demixing transition
Waterlike thermodynamic anomalies in a repulsive-step potential system
We report a computer-simulation study of the equilibrium phase diagram of a
three-dimensional system of particles with a repulsive step potential. The
phase diagram is obtained using free-energy calculations. At low temperatures,
we observe a number of distinct crystal phases. We show that at certain values
of the potential parameters the system exhibits the water-like thermodynamic
anomalies: density anomaly and diffusion anomaly. The anomalies disappear with
increasing the repulsive step width: their locations move to the region inside
the crystalline phase.Comment: 6 pages, 5 figure
Boundary lubrication properties of materials with expansive freezing
We have performed molecular dynamics simulations of solid-solid contacts
lubricated by a model fluid displaying many of the properties of water,
particularly its expansive freezing. Near the region where expansive freezing
occurs, the lubricating film remains fluid, and the friction force decreases
linearly as the shear velocity is reduced. No sign of stick-slip motion is
observed even at the lowest velocities. We give a simple interpretation of
these results, and suggest that in general good boundary lubrication properties
will be found in the family of materials with expansive freezing.Comment: Version to appear in Phys. Rev. Let
Configurational Entropy and Diffusivity of Supercooled Water
We calculate the configurational entropy S_conf for the SPC/E model of water
for state points covering a large region of the (T,rho) plane. We find that (i)
the (T,rho) dependence of S_conf correlates with the diffusion constant and
(ii) that the line of maxima in S_conf tracks the line of density maxima. Our
simulation data indicate that the dynamics are strongly influenced by S_conf
even above the mode-coupling temperature T_MCT(rho).Comment: Significant update of reference
Instantaneous Normal Mode Analysis of Supercooled Water
We use the instantaneous normal mode approach to provide a description of the
local curvature of the potential energy surface of a model for water. We focus
on the region of the phase diagram in which the dynamics may be described by
the mode-coupling theory. We find, surprisingly, that the diffusion constant
depends mainly on the fraction of directions in configuration space connecting
different local minima, supporting the conjecture that the dynamics are
controlled by the geometric properties of configuration space. Furthermore, we
find an unexpected relation between the number of basins accessed in
equilibrium and the connectivity between them.Comment: 5 pages, 4 figure
Supercooled confined water and the Mode Coupling crossover temperature
We present a Molecular Dynamics study of the single particle dynamics of
supercooled water confined in a silica pore. Two dynamical regimes are found:
close to the hydrophilic substrate molecules are below the Mode Coupling
crossover temperature, , already at ambient temperature. The water closer
to the center of the pore (free water) approaches upon supercooling as
predicted by Mode Coupling Theories. For free water the crossover temperature
and crossover exponent are extracted from power-law fits to both the
diffusion coefficient and the relaxation time of the late region.Comment: To be published, Phys. Rev. Lett., 4 pages, 3 figures, revTeX, minor
changes in the figures, references added, changes in the tex
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