No Arabic abstract
The dynamics of soft colloids in solutions is characterized by internal collective motion as well as center-of-mass diffusion. Using neutron scattering we demonstrate that the competition between the relaxation processes associated with these two degrees of freedom results in strong dependence of dynamics and structure on colloid concentration, c, even well below the overlap concentration c*. We show that concurrent with increasing inter-particle collisions, substantial structural dehydration and slowing-down of internal dynamics occur before geometrically defined colloidal overlap develops. While previous experiments have shown that the average size of soft colloids changes very little below c*, we find a marked change in both the internal structure and internal dynamics with concentration. The competition between these two relaxation processes gives rise to a new dynamically-defined dilute threshold concentration well below c*.
Stabilization and dispersion of electrical charge by colloids in non-polar media, such as nano-particles or inverse micelles, is significant for a variety of chemical and technological applications, ranging from drug delivery to e-ink. Many applications require knowledge about concentrations near the solid|liquid interface and the bulk, particularly in media where colloids exhibit spontaneous charging properties. By modification of the mean field equations to include the finite size effects that are typical in concentrated electrolytes along with disproportionation kinetics, and by considering high potentials, it is possible to evaluate the width of the condensed double layers near planar electrodes and the bulk concentrations of colloids at steady state. These quantities also provide an estimate of the minimum initial colloid concentration that is required to support electroneutrality in the dispersion bulk, and thus provide insights into the quasi-steady state currents that have been observed in inverse micellar media.
We use molecular dynamics simulations in a constant potential ensemble to study the effects of solution composition on the electrochemical response of a double layer capacitor. We find that the capacitance first increases with ion concentration following its expected ideal solution behavior, but decreases upon approaching a pure ionic liquid in agreement with recent experimental observations. The non-monotonic behavior of the capacitance as a function of ion concentration results from the competition between the independent motion of solvated ions in the dilute regime and solvation fluctuations in the concentrated regime. Mirroring the capacitance, we find that the characteristic decay length of charge density correlations away from the electrode is also non-monotonic. The correlation length first decreases with ion concentration as a result of better electrostatic screening but increases with ion concentration as a result of enhanced steric interactions. When charge fluctuations induced by correlated ion-solvent fluctuations are large relative to those induced by the pure ionic liquid, such capacitive behavior is expected to be generic.
Using Monte Carlo simulations, we investigate the structural characteristics of an interacting hard sphere system with shifted charge to elucidate the effect of the non-centrosymmetric interaction on its phase behavior. Two different phase transitions are identified for this model system. Upon increasing the volume fraction, an abrupt liquid-to-crystal transition first occurs at a significantly lower volume fraction in comparison to that of the centro-charged system. This is due to the stronger effective inter-particle repulsion caused by the additional charge anisotropy. Moreover, within the crystal state at higher volume fraction, the system further undergoes a continuous disorder-to-order transition with respect to the charge orientation. Detailed analyses in this work disclose the nature of these transitions, and orientation fluctuation may cause non-centrosymmetric unit cells. The dependence of crystal formation and orientational ordering on temperature was also examined. These findings indicate that the non-centrosymmetric interaction in this work results in additional freedoms to fine-tune the phase diagram and increase the functionalities of materials. Moreover, these model studies are essential to advance our future understanding regarding the fundamental physiochemical properties of novel Janus colloidal particles and protein crystallization conditions.
We describe a tracer in a bath of soft Brownian colloids by a particle coupled to the density field of the other bath particles. From the Dean equation, we derive an exact equation for the evolution of the whole system, and show that the density field evolution can be linearized in the limit of a dense bath. This linearized Dean equation with a tracer taken apart is validated by the reproduction of previous results on the mean-field liquid structure and transport properties. Then, the tracer is submitted to an external force and we compute the density profile around it, its mobility and its diffusion coefficient. Our results exhibit effects such as bias enhanced diffusion that are very similar to those observed in the opposite limit of a hard core lattice gas, indicating the robustness of these effects. Our predictions are successfully tested against molecular dynamics simulations.
The semilocal meta generalized gradient approximation (MGGA) for the exchange-correlation functional of Kohn-Sham (KS) density functional theory can yield accurate ground-state energies simultaneously for atoms, molecules, surfaces, and solids, due to the inclusion of kinetic energy density as an input. We study for the first time the effect and importance of the dependence of MGGA on the kinetic energy density through the dimensionless inhomogeneity parameter, $alpha$, that characterizes the extent of orbital overlap. This leads to a simple and wholly new MGGA exchange functional, which interpolates between the single-orbital regime, where $alpha=0$, and the slowly varying density regime, where $alpha approx 1$, and then extrapolates to $alpha to infty$. When combined with a variant of the Perdew-Burke-Erzerhof (PBE) GGA correlation, the resulting MGGA performs equally well for atoms, molecules, surfaces, and solids.