Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userLayering, freezing and re-entrant melting of hard spheres in soft confinement
190
0
0.0
(
0
)
Ask ChatGPT about the research
No Arabic abstract
Confinement can have a dramatic effect on the behavior of all sorts of particulate systems and it therefore is an important phenomenon in many different areas of physics and technology. Here, we investigate the role played by the softness of the confining potential. Using grand canonical Monte Carlo simulations, we determine the phase diagram of three-dimensional hard spheres that in one dimension are constrained to a plane by a harmonic potential. The phase behavior depends strongly on the density and on the stiffness of the harmonic confinement. Whilst we find the familiar sequence of confined hexagonal and square-symmetric packings, we do not observe any of the usual intervening ordered phases. Instead, the system phase separates under strong confinement, or forms a layered re-entrant liquid phase under weaker confinement. It is plausible that this behavior is due to the larger positional freedom in a soft confining potential and to the contribution that the confinement energy makes to the total free energy. The fact that specific structures can be induced or suppressed by simply changing the confinement conditions (e.g. in a dielectrophoretic trap) is important for applications that involve self-assembled structures of colloidal particles.
rate research
Read More
We studied the phase behavior of charged and sterically stabilized colloids using confocal microscopy in a less polar solvent (dielectric constant 5.4). Upon increasing the colloid volume fraction we found a transition from a fluid to a body centered cubic crystal at 0.0415+/-0.0005, followed by re-entrant melting at 0.1165+/-0.0015. A second crystal of different symmetry, random hexagonal close-packed, was formed at a volume fraction around 0.5, similar to that of hard spheres. We attribute the intriguing phase behavior to particle interactions that depend strongly on volume fraction, mainly due to changes in the colloid charge. In this low polarity system the colloids acquire charge through ion adsorption. The low ionic strength leads to fewer ions per colloid at elevated volume fractions and consequently a density-dependent colloid charge.
Re-entrant melting (in which a substances melting point starts to decrease beyond a certain pressure) is believed to be an unusual phenomenon. Among the elements, it has so far only been observed in a very limited number of species, e.g., the alkali metals. Our density functional theory calculations reveal that this behavior actually extends beyond alkali metals to include magnesium, which also undergoes re-entrant melting, though at the much higher pressure of ~300 GPa. We find that the origin of re-entrant melting is the faster softening of interatomic interactions in the liquid phase than in the solid, as pressure rises. We propose a simple approach to estimate pressure-volume relations and show that this characteristic softening pattern is widely observed in metallic elements. We verify this prediction in the case of aluminum by finding re-entrant melting at ~4000 GPa. These results suggest that re-entrant melting may be a more universal feature than previously thought.
Water shapes and defines the properties of biological systems. Therefore, understanding the nature of the mutual interaction between water and biological systems is of primary importance for a proper assessment of biological activity and the development of new drugs and vaccines. A handy way to characterize the interactions between biological systems and water is to analyze their impact on water density and dynamics in the proximity of the interfaces. It is well established that water bulk density and dynamical properties are recovered at distances in the order of $sim1$~nm from the surface of biological systems. Such evidence led to the definition of emph{hydration} water as the thin layer of water covering the surface of biological systems and affecting-defining their properties and functionality. Here, we review some of our latest contributions showing that phospholipid membranes affect the structural properties and the hydrogen bond network of water at greater distances than the commonly evoked $sim1$~nm from the membrane surface. Our results imply that the concept of hydration water should be revised or extended, and pave the way to a deeper understanding of the mutual interactions between water and biological systems.
We show that a system of particles interacting through the exp-6 pair potential, commonly used to describe effective interatomic forces under high compression, exhibits anomalous melting features such as reentrant melting and a rich solid polymorphism, including a stable BC8 crystal. We relate this behavior to the crossover, with increasing pressure, between two different regimes of local order that are associated with the two repulsive length scales of the potential. Our results provide a unifying picture for the high-pressure melting anomalies observed in many elements and point out that, under extreme conditions, atomic systems may reveal surprising similarities with soft matter.
We investigate the behavior of hydrated sulfonated polysulfones over a range of ion contents through differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and molecular dynamics (MD) simulations. Experimental evidence shows that at comparable ion contents, the spacing between the ionic groups along the polymer backbone can significantly impact the amount of melting water present in the polymer. When we only consider water molecules that can hydrogen bond to four neighboring water molecules as the melting water, the MD simulation results are found to agree with the experimental data. The states of water measured by DSC can therefore be described as aggregated (or bulk-like) for the melting component, and isolated for the nonmelting part. Using this physical picture, a polymer with more aggregated ions has a higher content of melting water, while a polymer at the same ion content but with more dispersed ions has a lower content of melting water. Therefore, ions should be well dispersed to minimize the amount of bulk-like water in ionic polymer membranes.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
