Journal
CHEMICAL PHYSICS LETTERS
Volume 479, Issue 4-6, Pages 173-183Publisher
ELSEVIER
DOI: 10.1016/j.cplett.2009.07.077
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Funding
- German Excellence Initiative via the Nanosystems Initiative Munich (NIM)
- Elite Netzwerk Bayern (CompInt)
- Deutsche Forschungsgemeinschaft (DFG) [NE 801/4]
- Ministry for Economy and Technology (BMWi)
- IDB [36/1/339]
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Classical force fields for molecular simulations of aqueous electrolytes are still controversial. We study alkali and halide ions at the air/water interface using novel non-polarizable force fields that were optimized based on bulk thermodynamics. In qualitative agreement with polarizable force-field simulations, ion repulsion from the interface decreases with increasing ion size. Iodide is even enhanced at the interface, which is rationalized by hydrophobic solvation at the interface, but exhibits a smaller surface propensity than in previous polarizable simulations. Surprisingly, lithium is less repelled than other cations because of its tightly bound hydration shell. A generalized Poisson-Boltzmann approach that includes ionic potentials of mean force from simulation almost quantitatively matches experimental interfacial tension increments for 1 molar sodium halides and alkali chlorides. We conclude that properly optimized non-polarizable force fields are transferable to interfacial environments and hold the potential for unravelling non-specific effects even in biological situations involving peptidic surfaces. (c) 2009 Elsevier B.V. All rights reserved.
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