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Specific cation effects at aqueous solution-vapor interfaces: Surfactant-like behavior of Li+ revealed by experiments and simulations

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Parry,  Jonathan
Department 'Resilience and Transformation in Eurasia', MPI for Social Anthropology, Max Planck Society;

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Stern,  Elsbeth
Center for Educational Research, Max Planck Institute for Human Development, Max Planck Society;

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Makowski,  Marcin
Dept. Butt: Physics at Interfaces, MPI for Polymer Research, Max Planck Society;

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Winter,  Bernd
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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引用

Perrine, K. A., Parry, J., Stern, E., Spyk, M. H. C. V., Makowski, M., Winter, B., Tobias, D. J., & Hemminger, J. C. (2017). Specific cation effects at aqueous solution-vapor interfaces: Surfactant-like behavior of Li+ revealed by experiments and simulations. Proceedings of the National Academy of Sciences of the USA. doi:10.1073/pnas.1707540114.


引用: https://hdl.handle.net/11858/00-001M-0000-002D-89C6-B
要旨
It is now well established by numerous experimental and computational studies that the adsorption propensities of inorganic anions conform to the Hofmeister series. The adsorption propensities of inorganic cations, such as the alkali metal cations, have received relatively little attention. Here we use a combination of liquid-jet X-ray photoelectron experiments and molecular dynamics simulations to investigate the behavior of K+ and Li+ ions near the interfaces of their aqueous solutions with halide ions. Both the experiments and the simulations show that Li+ adsorbs to the aqueous solution−vapor interface, while K+ does not. Thus, we provide experimental validation of the “surfactant-like” behavior of Li+ predicted by previous simulation studies. Furthermore, we use our simulations to trace the difference in the adsorption of K+ and Li+ ions to a difference in the resilience of their hydration shells.