Fluctuation enhancement of ion diffusivity in liquids

文献情報

出版日 2017-11-15

DOI 10.1039/C7CP07170A

インパクトファクター 3.676

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要旨

The diffusivity of ions in liquid solutions is known either to decrease with an increase in the ion size or to have a single maximum depending on the ion size. This article presents evidence for the appearance of multiple maxima and thus multiple ion sizes with enhanced diffusivity. This is caused by destabilization of the ion solvation shell and only happens at the ion radii that correspond to changes of the ion coordination number, which happen with an increase in the ion size. Solvation shell fluctuations are activated which leads to additional ion motion with rearrangement of the shell. A theoretical model of this effect is derived and is shown to be in good agreement with molecular dynamics and experimental data. This result rewrites a long standing picture of ion transport as a function of ion size and introduces a new possibility in the search for highly conductive systems.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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.