Ion hydration: linking self-diffusion and reorientational motion to water structure
Literature Information
Seishi Shimizu
Ions affect the self-diffusion and relaxation of water. Such ion-induced changes of water dynamics have long been rationalized in terms of the change of the water structure around the ions. The aim of this paper is to establish a link between dynamics and the “water structure” on the basis of the extended jump (EJ) model for the reorientational motion of water, Eyring's transition state theory of the self-diffusion of water, and the statistical thermodynamic preferential solvation theory developed from the Kirkwood–Buff (KB) theory. Through the synthesis of the above three, we formulate a scheme to correlate the ion-induced water dynamics changes to the water structure. With this new formulation, it is shown that chaotropic or negatively hydrated ions preferentially bind the transition state of water motion thereby stabilizing the transition state, whereas the exclusion of kosmotropes or positively hydrated ions suppresses the formation of the transition state. The ion effects on water dynamics are thus analyzed in a unified manner in terms of KB integrals, which represent the (averaged) “structures” of water.
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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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