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It is well-known that room temperature ionic liquids (RTILs) often adopt a charge-separated layered structure, i.e., with alternating cation- and anion-rich layers, at electrified interfaces. However, the dynamic response of the layered structure to temporal variations in applied potential is not well understood. We used in situ, real-time X-ray reflectivity (XR) to study the potential-dependent electric double layer (EDL) structure of an imidazolium-based RTIL on charged epitaxial graphene during potential cycling as a function of temperature. The results suggest that the graphene-RTIL interfacial structure is bistable in which the EDL structure at any intermediate potential can be described by the combination of two extreme-potential structures whose proportions vary depending on the polarity and magnitude of the applied potential. This picture is supported by the EDL structures obtained by fully atomistic molecular dynamics (MD) simulations at various static potentials. The potential-driven transition between the two structures is characterized by an increasing width but with an approximately fixed hysteresis magnitude as a function of temperature. The results are consistent with the coexistence of distinct anion and cation adsorbed structures separated by an energy barrier (~0.15 eV).
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Ionic liquids are a special category of molten salts with melting points near ambient temperatures or by convention below 100 C. Owing to their numerous valuable physicochemical properties as bulk liquids, solvents, at surfaces and in confined environments, ILs have attracted increasing attention in both academic and industrial communities in a variety of application areas involving physics, chemistry, material science and engineering. Due to their nearly limitless number of combinations of cation and anion pairs and mixtures with cosolvents, a molecular level understanding of their hierarchical structures and dynamics, requiring strategies to connect several length and time scales, is of crucial significance for rational design of ILs with desired properties, and thereafter refining their functional performance in applications. As an invaluable compliment to experiments from synthesis to characterization, computational modelling and simulations have significantly increased our understanding on how physicochemical and structural properties of ILs can be controlled by their underlying chemical and molecular structures. In this chapter, we will give examples from our own modelling work based on selected IL systems, with focus on imidazolium based and tetraalkylphosphonium orthoborate ILs, studied at several spatiotemporal scales in different environments and with particular attention to applications of high technological interest.
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The aim of this work is to study the problem of the existence of a fundamental relation between the interfacial tension of a system of two partially miscible liquids and the surface tensions of the pure substances. It is shown that these properties cannot be correlated from the physical point of view. However, an accurate relation between them may be developed using a mathematical artifact. In the light of this work, the basis of the empirical formula of Girifalco and Good is examined. The weakness of this formula as well as the approximation leading to it are exposed and discussed and, a new equation connecting interfacial and surface tensions is proposed.
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