Kavli Affiliate: David T. Limmer
| First 5 Authors: Franky Bernal, Amro Dodin, Constantine Kyprianou, David T. Limmer, Richard J. Saykally
| Summary:
Combining Deep-UV second harmonic generation spectroscopy with molecular
simulations, we confirm and quantify the specific adsorption of guanidinium
cations to the air-water interface. Using a Langmuir analysis and measurements
at multiple concentrations, we extract the Gibbs free energy of adsorption,
finding it larger than typical thermal energies. Molecular simulations clarify
the role of polarizability in tuning the thermodynamics of adsorption, and
establish the preferential parallel alignment of guanidinium at the air-water
interface. Guanidinium is the first polyatomic cation proven to exhibit a
propensity for the air-water interface. As such, these results expand on the
growing body of work on specific ion adsorption.
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