Molecular modeling of ions at interfaces: exploring similarities to hydrophobic solvation through the lens of induced aqueous interfacial fluctuations
Literature Information
Shu-Ching Ou, Di Cui, Sandeep Patel
Ion specific effects are ubiquitous in chemistry and biology. While ion specific effects in molecular simulations are generally explained as the result of an interplay between ionic hydration, non-electrostatic potentials and ionic polarizability, this perspective considers an alternative discussion of the coupling of ionic hydration and an interfacial solvent as a contributing component leading to differing interfacial stabilities amongst ions. Interfacially stable ions, characterized as such by minima in free energy profiles, induce larger interfacial fluctuations compared to non-interfacial active species, conferring more covariance entropy approaching the interface. Larger anions, particularly those that are modeled classically with low charge-density, behave as canonical hydrophobic solutes with respect to their solvent-mediated interactions with soft interfaces; whereas smaller anions and cations show no interfacially stable states, nor enhanced interfacial fluctuations. Underlying this phenomenon is the fundamental nature of the hydration shell structure, dynamics, and rigidity around the solutes.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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