167 research outputs found
Structure, phase behavior and inhomogeneous fluid properties of binary dendrimer mixtures
The effective pair potentials between different kinds of dendrimers in
solution can be well approximated by appropriate Gaussian functions. We find
that in binary dendrimer mixtures the range and strength of the effective
interactions depend strongly upon the specific dendrimer architecture. We
consider two different types of dendrimer mixtures, employing the Gaussian
effective pair potentials, to determine the bulk fluid structure and phase
behavior. Using a simple mean field density functional theory (DFT) we find
good agreement between theory and simulation results for the bulk fluid
structure. Depending on the mixture, we find bulk fluid-fluid phase separation
(macro-phase separation) or micro-phase separation, i.e., a transition to a
state characterized by undamped periodic concentration fluctuations. We also
determine the inhomogeneous fluid structure for confinement in spherical
cavities. Again, we find good agreement between the DFT and simulation results.
For the dendrimer mixture exhibiting micro-phase separation, we observe rather
striking pattern formation under confinement.Comment: 8 pages, 10 figure
Charge-induced conformational changes of dendrimers
We study the effect of chargeable monomers on the conformation of dendrimers
of low generation by computer simulations, employing bare Coulomb interactions.
The presence of the latter leads to an increase in size of the dendrimer due to
a combined effect of electrostatic repulsion and the presence of counterions
within the dendrimer, and also enhances a shell-like structure for the monomers
of different generations. In the resulting structures the bond-length between
monomers, especially near the center, will increase to facilitate a more
effective usage of space in the outer-regions of the dendrimer.Comment: 7 pages, 12 figure
Metastable Dynamics above the Glass Transition
The element of metastability is incorporated in the fluctuating nonlinear
hydrodynamic description of the mode coupling theory (MCT) of the liquid-glass
transition. This is achieved through the introduction of the defect density
variable into the set of slow variables with the mass density and
the momentum density . As a first approximation, we consider the case
where motions associated with are much slower than those associated with
. Self-consistently, assuming one is near a critical surface in the MCT
sense, we find that the observed slowing down of the dynamics corresponds to a
certain limit of a very shallow metastable well and a weak coupling between
and . The metastability parameters as well as the exponents
describing the observed sequence of time relaxations are given as smooth
functions of the temperature without any evidence for a special temperature. We
then investigate the case where the defect dynamics is included. We find that
the slowing down of the dynamics corresponds to the system arranging itself
such that the kinetic coefficient governing the diffusion of the
defects approaches from above a small temperature-dependent value .Comment: 38 pages, 14 figures (6 figs. are included as a uuencoded tar-
compressed file. The rest is available upon request.), RevTEX3.0+eps
Interplay Between Time-Temperature-Transformation and the Liquid-Liquid Phase Transition in Water
We study the TIP5P water model proposed by Mahoney and Jorgensen, which is
closer to real water than previously-proposed classical pairwise additive
potentials. We simulate the model in a wide range of deeply supercooled states
and find (i) the existence of a non-monotonic ``nose-shaped'' temperature of
maximum density line and a non-reentrant spinodal, (ii) the presence of a low
temperature phase transition, (iii) the free evolution of bulk water to ice,
and (iv) the time-temperature-transformation curves at different densities.Comment: RevTeX4, 4 pages, 4 eps figure
Nonlinear Hydrodynamics of a Hard Sphere Fluid Near the Glass Transition
We conduct a numerical study of the dynamic behavior of a dense hard sphere
fluid by deriving and integrating a set of Langevin equations. The statics of
the system is described by a free energy functional of the
Ramakrishnan-Yussouff form. We find that the system exhibits glassy behavior as
evidenced through stretched exponential decay and two-stage relaxation of the
density correlation function. The characteristic times grow with increasing
density according to the Vogel-Fulcher law. The wavenumber dependence of the
kinetics is extensively explored. The connection of our results with
experiment, mode coupling theory, and molecular dynamics results is discussed.Comment: 34 Pages, Plain TeX, 12 PostScript Figures (not included, available
on request
Harmonic Vibrational Excitations in Disordered Solids and the "Boson Peak"
We consider a system of coupled classical harmonic oscillators with spatially
fluctuating nearest-neighbor force constants on a simple cubic lattice. The
model is solved both by numerically diagonalizing the Hamiltonian and by
applying the single-bond coherent potential approximation. The results for the
density of states are in excellent agreement with each other. As
the degree of disorder is increased the system becomes unstable due to the
presence of negative force constants. If the system is near the borderline of
stability a low-frequency peak appears in the reduced density of states
as a precursor of the instability. We argue that this peak
is the analogon of the "boson peak", observed in structural glasses. By means
of the level distance statistics we show that the peak is not associated with
localized states
Equilibration times in numerical simulation of structural glasses: Comparing parallel tempering and conventional molecular dynamics
Generation of equilibrium configurations is the major obstacle for numerical
investigation of the slow dynamics in supercooled liquid states. The parallel
tempering (PT) technique, originally proposed for the numerical equilibration
of discrete spin-glass model configurations, has recently been applied in the
study of supercooled structural glasses. We present an investigation of the
ability of parallel tempering to properly sample the liquid configuration space
at different temperatures, by mapping the PT dynamics into the dynamics of the
closest local potential energy minima (inherent structures). Comparing the PT
equilibration process with the standard molecular dynamics equilibration
process we find that the PT does not increase the speed of equilibration of the
(slow) configurational degrees of freedom.Comment: 5 pages, 3 figure
Fermi surface of a system with strong valence fluctuations : evidence for a noninteger count of valence electrons in EuIr2Si2
We present de Haas-van Alphen (dHvA) measurements on an Eu-based valence-fluctuating system. EuIr2Si2 exhibits a temperature-dependent, noninteger europium valence with Eu2.8+ at low temperatures. The comparison of experimental results from our magnetic-torque experiments in fields up to 32 T and density functional theory band-structure calculations with localized 4f electrons shows that the best agreement is reached for a Fermi surface based on a valence of Eu2.8+. The calculated quantum-oscillation frequencies for Eu3+ instead cannot explain all the experimentally observed frequencies. The effective masses, derived from the temperature dependence of the dHvA oscillation amplitudes, show not only a significant enhancement with masses up to 11me (me being the free electron mass), but also a magnetic-field dependence of the heaviest mass. We attribute the formation of these heavy masses to strong correlation effects resulting from valence fluctuations of 4f electrons being strongly hybridized with conduction electrons. The increase of the heavy masses with magnetic field likely results from the onset of the expected field-induced valence crossover that enhances these valence fluctuations but does not alter the Fermi-surface topology in the field range studied
Inherent Structure Entropy of Supercooled Liquids
We present a quantitative description of the thermodynamics in a supercooled
binary Lennard Jones liquid via the evaluation of the degeneracy of the
inherent structures, i.e. of the number of potential energy basins in
configuration space. We find that for supercooled states, the contribution of
the inherent structures to the free energy of the liquid almost completely
decouples from the vibrational contribution. An important byproduct of the
presented analysis is the determination of the Kauzmann temperature for the
studied system. The resulting quantitative picture of the thermodynamics of the
inherent structures offers new suggestions for the description of equilibrium
and out-of-equilibrium slow-dynamics in liquids below the Mode-Coupling
temperature.Comment: 11 pages of Latex, 3 figure
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