title: Behavior of the Eigen form of hydronium at the air/water interface.
abstract: Surface affinity of hydro-nium was explored using umbrella sampling molecular dynamics simulations with a refined polarizable potential. The polarizable interaction potential of H(3)O(+) was reparametrized against accurate ab initio calculations for geometries including a water molecule approaching the Eigen cation from its oxygen side. Although there is no true hydrogen bonding with H(3)O(+) acting as an acceptor, respecting in the force field the very shallow ab initio minimum corresponding to this interaction leads to a decrease in surface propensity of hydronium compared to previous results. Qualitatively, the mild surface affinity and strong surface orientation of hydronium is, nevertheless, robustly predicted by various computational approaches, as well as by spectroscopic experiments.
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 16610 Prague 6, Czech Republic.
authors.forename: Barbara
authors.initials: B
authors.lastname: Jagoda-Cwiklik
authors.forename: Lukasz
authors.initials: L
authors.lastname: Cwiklik
authors.forename: Pavel
authors.initials: P
authors.lastname: Jungwirth