No Arabic abstract
This work shows that bulk ionic liquids (ILs) and their water solution can be conveniently investigated by synchrotron-based UV resonance Raman (UVRR) spectroscopy. The main advantages of this technique for the investigation of the local structure and intermolecular interactions in imidazolium-based ILs are presented and discussed. The unique tunability of synchrotron source allows one to selectively enhance in the Raman spectra the vibrational signals arising from the imidazolium ring. Such signals showed good sensitivity to the modifications induced in the local structure of ILs by i) the change of anion and ii) the progressively longer alkyl chain substitution on the imidazolium ring. Moreover, some UVRR signals are specifically informative on the effect induced by addition of water on the strength of cation-anion H-bonds in IL-water solutions. All of these results corroborate the potentiality of UVRR to retrieve information on the intermolecular interactions in IL-water solutions, besides the counterpart obtained by employing on these systems the spontaneous Raman scattering technique.
A simple non-local theoretical model is developed considering concentrated ionic surfactant solutions as regular ones. Their thermodynamics is described by the Cahn-Hilliard theory coupled with electrostatics. It is discovered that unstable solutions possess two critical temperatures, where the temperature coefficients of all characteristic lengths are discontinuous. At temperatures below the lower critical temperature ionic surfactant solutions separate into thin layers of oppositely charged liquids spread across the whole system and the electric potential is strictly periodic. At temperatures between the two critical temperatures separation can occur only near the solution surface thus leading to an oscillatory-decaying electric double layer. At temperatures above the higher critical temperature as well as in stable solutions there is no separation and the electric potential decays exponentially.
When analyzing the broadband absorption spectrum of liquid water (10^10 - 10^13 Hz), we find its relaxation-resonance features to be an indication of Frenkels translation-oscillation motion of particles, which is fundamentally inherent to liquids. We have developed a model of water structure, of which the dynamics is due to diffusion of particles, neutral H2O molecules and H3O+ and OH- ions - with their periodic localizations and mutual transformations. This model establishes for the first time a link between the dc conductivity, the Debye and the high frequency sub-Debye relaxations and the infrared absorption peak at 180 cm-1. The model reveals the characteristic times of the relaxations, 50 ps and 3 ps, as the lifetimes of water molecules and water ions, respectively. The model sheds light on the anomalous mobility of a proton and casts doubt on the long lifetime of a water molecule, 10 hours, commonly associated with autoionization.
Dynamics of a coarse-grained model for the room-temperature ionic liquid, 1-ethyl-3-methylimidazolium hexafluorophosphate, couched in the united-atom site representation are studied via molecular dynamics simulations. The dynamically heterogeneous behavior of the model resembles that of fragile supercooled liquids. At or close to room temperature, the model ionic liquid exhibits slow dynamics, characterized by nonexponential structural relaxation and subdiffusive behavior. The structural relaxation time, closely related to the viscosity, shows a super-Arrhenius behavior. Local excitations, defined as displacement of an ion exceeding a threshold distance, are found to be mainly responsible for structural relaxation in the alternating structure of cations and anions. As the temperature is lowered, excitations become progressively more correlated. This results in the decoupling of exchange and persistence times, reflecting a violation of the Stokes-Einstein relation.
Bulk properties of ionic liquid crystals are investigated using density functional theory. The liquid crystal molecules are represented by ellipsoidal particles with charges located in their center or at their tails. Attractive interactions are taken into account in terms of the Gay-Berne pair potential. Rich phase diagrams involving vapor, isotropic and nematic liquid, as well as smectic phases are found. The dependence of the phase behavior on various parameters such as the length of the particles and the location of charges on the particles is studied.
The study of liquid-liquid phase transition has attracted considerable attention. One interesting example of such phenomenon is phosphorus for which the existence a first-order phase transition between a low density insulating molecular phase and a conducting polymeric phase has been experimentally established. In this paper, we model this transition by an ab-initio quality molecular dynamics simulation and explore a large portion of the liquid section of the phase diagram. We draw the liquid-liquid coexistence curve and determine that it terminates into a second-order critical point. Close to the critical point, large coupled structure and electronic structure fluctuations are observed.