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Register a new userControlling the interfacial and bulk concentrations of spontaneously charged colloids in non-polar media
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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.
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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*.
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.
The ionic composition and pair correlations in fluid phases of realistically salt-free charged colloidal sphere suspensions are calculated in the primitive model. We obtain the number densities of all ionic species in suspension, including low-molecular weight microions, and colloidal macroions with acidic surface groups, from a self-consistent solution of a coupled physicochemical set of nonlinear algebraic equations and non-mean-field liquid integral equations. Here, we study suspensions of colloidal spheres with sulfonate or silanol surface groups, suspended in demineralized water that is saturated with carbon dioxide under standard atmosphere. The only input required for our theoretical scheme are the acidic dissociation constants pKa, and effective sphere diameters of all involved ions. Our method allows for an ab initio calculation of colloidal bare and effective charges, at high numerical efficiency.
Molecular dynamics (MD) simulations are used to investigate $^1$H nuclear magnetic resonance (NMR) relaxation and diffusion of bulk $n$-C$_5$H$_{12}$ to $n$-C$_{17}$H$_{36}$ hydrocarbons and bulk water. The MD simulations of the $^1$H NMR relaxation times $T_{1,2}$ in the fast motion regime where $T_1 = T_2$ agree with measured (de-oxygenated) $T_2$ data at ambient conditions, without any adjustable parameters in the interpretation of the simulation data. Likewise, the translational diffusion $D_T$ coefficients calculated using simulation configurations are well-correlated with measured diffusion data at ambient conditions. The agreement between the predicted and experimentally measured NMR relaxation times and diffusion coefficient also validate the forcefields used in the simulation. The molecular simulations naturally separate intramolecular from intermolecular dipole-dipole interactions helping bring new insight into the two NMR relaxation mechanisms as a function of molecular chain-length (i.e. carbon number). Comparison of the MD simulation results of the two relaxation mechanisms with traditional hard-sphere models used in interpreting NMR data reveals important limitations in the latter. With increasing chain length, there is substantial deviation in the molecular size inferred on the basis of the radius of gyration from simulation and the fitted hard-sphere radii required to rationalize the relaxation times. This deviation is characteristic of the local nature of the NMR measurement, one that is well-captured by molecular simulations.
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Yujin Tong
, Tobias Kampfrath
, R. Kramer Campen (Fritz Habern Institute of the Max Planck Society
2017
Most properties of liquid water are determined by its hydrogen-bond network. Because forming an aqueous interface requires termination of this network, one might expect the molecular level properties of interfacial water to markedly differ from water in bulk. Intriguingly, much prior experimental and theoretical work has found that, from the perspective of their time-averaged structure and picosecond structural dynamics, hydrogen-bonded OH groups at an air/water interface behave the same as hydrogen-bonded OH groups in bulk liquid water. Here we report the first experimental observation of interfacial waters libration (i.e. frustrated rotation) using the laser-based technique vibrational sum frequency spectroscopy. We find this mode has a frequency of 834 cm$^{-1}$, $approx 165$ cm$^{-1}$ higher than in bulk liquid water at the same temperature and similar to bulk ice. Because libration frequency is proportional to the stiffness of waters rotational potential, this increase suggests that one effect of terminating bulk waters hydrogen bonding network at the air/water interface is retarding rotation of water around intact hydrogen bonds. Because in bulk liquid water the libration plays a key role in stabilizing reaction intermediates and dissipating excess vibrational energy, we expect the ability to probe this mode in interfacial water to open new perspectives on the kinetics of heterogeneous reactions at aqueous interfaces.
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