384 research outputs found
Metastability, Mode Coupling and the Glass Transition
Mode coupling theory (MCT) has been successful in explaining the observed
sequence of time relaxations in dense fluids. Previous expositions of this
theory showing this sequence have required the existence of an ideal glass
transition temperature . Recent experiments show no evidence of . We
show here how the theory can be reformulated, in a fundamental way, such that
one retains this sequence of relaxation behaviors but with a smooth temperature
dependence and without any indication of . The key ingredient in the
reformulation is the inclusion of the metastable nature of the glass transition
problem through a coupling of the mass density to the defect density. A main
result of our theory is that the exponents governing the sequence of time
relaxations are weak functions of the temperature in contrast to the results
from conventional MCT.Comment: 14 pages (2 figures upon request), REVTEX
Influence of the Environment Fluctuations on Incoherent Neutron Scattering Functions
In extending the conventional dynamic models, we consider a simple model to
account for the environment fluctuations of particle atoms in a protein system
and derive the elastic incoherent structure factor (EISF) and the incoherent
scattering correlation function C(Q,t) for both the jump dynamics between sites
with fluctuating site interspacing and for the diffusion inside a fluctuating
sphere. We find that the EISF of the system (or the normalized elastic
intensity) is equal to that in the absence of fluctuations averaged over the
distribution of site interspacing or sphere radius a. The scattering
correlation function is ,
where the average is taken over the Q-dependent effective distribution of
relaxation rates \lambda_n(a) and \psi(t) is the correlation function of the
length a. When \psi(t)=1, the relaxation of C(Q,t) is exponential for the jump
dynamics between sites (since \lambda_n(a) is independent of a) while it is
nonexponential for diffusion inside a sphere.Comment: 7 pages, 7 eps figure
On the origin of the Boson peak in globular proteins
We study the Boson Peak phenomenology experimentally observed in globular
proteins by means of elastic network models. These models are suitable for an
analytic treatment in the framework of Euclidean Random Matrix theory, whose
predictions can be numerically tested on real proteins structures. We find that
the emergence of the Boson Peak is strictly related to an intrinsic mechanical
instability of the protein, in close similarity to what is thought to happen in
glasses. The biological implications of this conclusion are also discussed by
focusing on a representative case study.Comment: Proceedings of the X International Workshop on Disordered Systems,
Molveno (2006
Evidence of coexistence of change of caged dynamics at Tg and the dynamic transition at Td in solvated proteins
Mossbauer spectroscopy and neutron scattering measurements on proteins
embedded in solvents including water and aqueous mixtures have emphasized the
observation of the distinctive temperature dependence of the atomic mean square
displacements, , commonly referred to as the dynamic transition at some
temperature Td. At low temperatures, increases slowly, but it assume
stronger temperature dependence after crossing Td, which depends on the
time/frequency resolution of the spectrometer. Various authors have made
connection of the dynamics of solvated proteins including the dynamic
transition to that of glass-forming substances. Notwithstanding, no connection
is made to the similar change of temperature dependence of obtained by
quasielastic neutron scattering when crossing the glass transition temperature
Tg, generally observed in inorganic, organic and polymeric glass-formers.
Evidences are presented to show that such change of the temperature dependence
of from neutron scattering at Tg is present in hydrated or solvated
proteins, as well as in the solvents used unsurprisingly since the latter is
just another organic glass-formers. The obtained by neutron scattering at
not so low temperatures has contributions from the dissipation of molecules
while caged by the anharmonic intermolecular potential at times before
dissolution of cages by the onset of the Johari-Goldstein beta-relaxation. The
universal change of at Tg of glass-formers had been rationalized by
sensitivity to change in volume and entropy of the beta-relaxation, which is
passed onto the dissipation of the caged molecules and its contribution to
. The same rationalization applies to hydrated and solvated proteins for
the observed change of at Tg.Comment: 28 pages, 10 figures, 1 Tabl
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
Metastable Dynamics of the Hard-Sphere System
The reformulation of the mode-coupling theory (MCT) of the liquid-glass
transition which incorporates the element of metastability is applied to the
hard-sphere system. It is shown that the glass transition in this system is not
a sharp one at the special value of the density or the packing fraction, which
is in contrast to the prediction by the conventional MCT. Instead we find that
the slowing down of the dynamics occurs over a range of values of the packing
fraction. Consequently, the exponents governing the sequence of time
relaxations in the intermediate time regime are given as functions of packing
fraction with one additional parameter which describes the overall scale of the
metastable potential energy for defects in the hard-sphere system. Implications
of the present model on the recent experiments on colloidal systems are also
discussed.Comment: 21 pages, 5 figures (available upon request), RevTEX3.0, JFI
Preprint
Recommended from our members
Trapping and hysteresis in two-phase flow in porous media: A pore-network study
Abstract: Several models for two-phase flow in porous media identify trapping and connectivity of fluids as an important contribution to macroscale hysteresis. This is especially true for hysteresis in relative permeabilities. The trapping models propose trajectories from the initial saturation to the end saturation in various ways and are often based on experiments or pore-network model results for the endpoints. However, experimental data or pore-scale model results are often not available for the trajectories, that is, the fate of the connectivity of the fluids while saturation changes. Here, using a quasi static pore-network model, supported by a set of pore-scale laboratory experiments, we study how the topology of the fluids changes during drainage and imbibition including first, main and scanning curves. We find a strong hysteretic behavior in the relationship between disconnected nonwetting fluid saturation and the wetting fluid saturation in a water-wet medium. The coalescence of the invading nonwetting phase with the existing disconnected nonwetting phase depends critically on the presence (or lack thereof) of connected nonwetting phase at the beginning of the drainage process as well as on the pore geometry. This dependence involves a mechanism we refer to as reversible corner filling. This mechanism can also be seen in laboratory experiments in volcanic tuff. The impact of these pore-network model results on existing macroscopic models is discussed.Keywords: hysteresis, trapping, two-phase flow, fluid topology, pore geometry, pore networ
The dynamic crossover in water does not require bulk water
Many of the anomalous properties of water may be explained by invoking a second critical point that terminates the coexistence line between the low- and high-density amorphous states in the liquid. Direct experimental evidence of this point, and the associated polyamorphic liquid–liquid transition, is elusive as it is necessary for liquid water to be cooled below its homogeneous-nucleation temperature. To avoid crystallization, water in the eutectic LiCl solution has been studied but then it is generally considered that “bulk” water cannot be present. However, recent computational and experimental studies observe cooperative hydration in which case it is possible that sufficient hydrogen-bonded water is present for the essential characteristics of water to be preserved. For femtosecond optical Kerr-effect and nuclear magnetic resonance measurements, we observe in each case a fractional Stokes–Einstein relation with evidence of the dynamic crossover appearing near 220 K and 250 K respectively. Spectra obtained in the glass state also confirm the complex nature of the hydrogen-bonding modes reported for neat room-temperature water and support predictions of anomalous diffusion due to “worm-hole” structure
- …