Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 114, Issue 51, Pages 13363-13368Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1707540114
Keywords
ion adsorption; air-water interface; specific ion effects; Hofmeister series; aqueous ionic solvation
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Funding
- National Science Foundation [CHE-0909227]
- Atmospheric Integrated Research at University of California, Irvine (AirUCI) Organized Research Unit
- Office of Science, Office of Basic Energy Sciences, of the US Department of Energy [DE-AC02-05CH11231]
- Deutsche Forschungsgemeinschaft through Collaborative Research Center [1109]
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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.
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