The thermodynamic and electrochemical properties of ionic liquids produce a broad spectrum of unconventional phenomena both microscopically and macroscopically. However, despite numerous theoretical and experimental studies, the fundamental roles of the relevant interactions such as electrostatic interactions and hydrogen bonding often remain unclear at the molecular level. The complexity of the molecular interactions typically increases when ionic liquids dissolve polymers or polar substances such as water. Accordingly, recent studies have revealed new features of ionic liquids. Further insights into the role of the molecular polarity of ionic liquids are required. This article presents an overview of the important phenomena of ionic liquids concerning soft‐matter sciences based on selected experimental and theoretical studies. We focus on the effect of the dielectric response of ionic liquids to distinguish ionic liquids from common inorganic salts, such as alkali metal halides.
Understanding dissolution kinetics is essential for predicting and mitigating materials corrosion; however, many mechanistic details still remain enigmatic. Examples include the evolution of solvation properties of ions and nature of electron transfer during dissolution. In this work, we integrate high-fidelity first-principles calculations based on grand-canonical density functional theory (DFT) and mesoscale simulations to predict dissolution kinetics of aluminum metal in acidic conditions. First, we show that the inclusion of an explicit solvation shell is crucial for accurately predicting the redox potential of metal dissolution. Second, we show that metal dissolution is governed by two kinetically limited processes, which are associated with the metal-metal bond breaking and ion diffusion within the electric double layer. Interestingly, it is found that kinetics and thermodynamics of these processes can be described with a simple model functionally based on Marcus theory, and their relative importance can be switched, depending on the applied potentials. Third, we show how dissolution kinetics derived from DFT is integrated with mesoscale simulations to elucidate the role of microstructure on the global metal dissolution. Comparison with experimental measurements will also be discussed.
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and was supported with Laboratory Directed Research and Development funding under Project 20-SI-004.
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