title: Bulk versus interfacial aqueous solvation of dicarboxylate dianions.
abstract: Solvation of dicarboxylate dianions of varying length of the aliphatic chain in water clusters and in extended aqueous slabs was investigated using photoelectron spectroscopy and molecular dynamics simulations. Photoelectron spectra of hydrated succinate, adipate, and tetradecandioic dianions with up to 20 water molecules were obtained. Even-odd effects were observed as a result of the alternate solvation mode of the two negative charges with increasing solvent numbers. The competition between hydrophilic interactions of the charged carboxylate groups and hydrophobic interactions of the aliphatic chain leads to conformation changes in large water clusters containing dicarboxylates bigger than adipate. It also leads to a transition from bulk aqueous solvation of small dicarboxylates to solvation at the water/vapor interface of the larger ones. Whereas oxalate and adipate solvate in the inner parts of the aqueous slab, suberate and longer dicarboxylate dianions have a strong propensity to the surface. This transition also has consequences for the folding of the flexible aliphatic chain and for the structure of aqueous solvation shells around the dianions.
authors.affiliation: Contribution from the Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nam. 2, 16610 Prague 6, Czech Republic.
authors.forename: Babak
authors.initials: B
authors.lastname: Minofar
authors.forename: Martin
authors.initials: M
authors.lastname: Mucha
authors.forename: Pavel
authors.initials: P
authors.lastname: Jungwirth
authors.forename: Xin
authors.initials: X
authors.lastname: Yang
authors.forename: You-Jun
authors.initials: YJ
authors.lastname: Fu
authors.forename: Xue-Bin
authors.initials: XB
authors.lastname: Wang
authors.forename: Lai-Sheng
authors.initials: LS
authors.lastname: Wang