Ion spatial distributions at the liquid-vapor interface of aqueous potassium fluoride solutions

Brown, M A; D'Auria, R; Kuo, I W; Krisch, M J; Starr, D E; Bluhm, H; Tobias, D J; Hemminger, J C

doi:10.1039/b807041e

Title: Ion spatial distributions at the liquid-vapor interface of aqueous potassium fluoride solutions

Journal Article · Wed Apr 23 00:00:00 EDT 2008 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/b807041e· OSTI ID:945895

Brown, M A; D'Auria, R; Kuo, I W; Krisch, M J; Starr, D E; Bluhm, H; Tobias, D J; Hemminger, J C

X-ray photoemission spectroscopy operating under ambient pressure conditions is used to probe ion distributions throughout the interfacial region of a free-flowing aqueous liquid micro-jet of 6 M potassium fluoride. Varying the energy of the ejected photoelectrons by carrying out experiments as a function of x-ray wavelength measures the composition of the aqueous-vapor interfacial region at various depths. The F{sup -} to K{sup +} atomic ratio is equal to unity throughout the interfacial region to a depth of 2 nm. The experimental ion profiles are compared with the results of a classical molecular dynamics simulation of a 6 M aqueous KF solution employing polarizable potentials. The experimental results are in qualitative agreement with the simulations when integrated over an exponentially decaying probe depth characteristic of an APPES experiment. First principles molecular dynamics simulations have been used to calculate the potential of mean force for moving a fluoride anion across the air-water interface. The results show that the fluoride anion is repelled from the interface, and this is consistent with the depletion of F{sup -} at the interface revealed by the APPES experiment and polarizable force field-based molecular dynamics simulation. Together, the APPES and MD simulation data provide a detailed description of the aqueous-vapor interface of alkali fluoride systems. This work offers the first direct observation of the ion distribution at a potassium fluoride aqueous solution interface. The current experimental results are compared to those previously obtained for saturated solutions of KBr and KI to underscore the strong difference in surface propensity between soft/large and hard/small halide ions in aqueous solution.

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Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: W-7405-ENG-48

OSTI ID:: 945895

Report Number(s):: LLNL-JRNL-403423; TRN: US0901123

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 10, Issue 32; ISSN 1463-9076

Country of Publication:: United States

Language:: English

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Title: Ion spatial distributions at the liquid-vapor interface of aqueous potassium fluoride solutions

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