title: Dynamical Dimension to the Hofmeister Series: Insights from First-Principles Simulations.
abstract: A systematic characterization of the competing kosmotropic and chaotropic effects of a series of divalent salts on the aqueous H-bonding structure by means of first-principles molecular dynamics simulations is presented. The structural properties are quantified by means of experimental and computed (1) H NMR chemical shifts, whereby the local environments of cations and anions can be discriminated. Complementary to the well-established structural features, a dynamical aspect is added to the concept of kosmotropes and chaotropes. The H-bond dynamics, quantified in terms of the H-bonding autocorrelation functions, shows a good correlation with the structural kosmotropic and chaotropic modifications, which are commonly referred to as the Hofmeister series. The considerably enhanced (reduced) fluctuations of the H-bonding network in the hydration shells around the anions (cations) are a complementary dynamical dimension to the concept of kosmotropic/chaotropic behavior of solvated ions.
authors: Institut für Chemie, Martin-Luther-Universität Halle-Wittenberg, Von-Danckelmann-Platz 4, 06120, Halle (Saale), Germany.|Physics Department, Freie Universität Berlin, Arnimallee 14, 14195, Berlin, Germany.
authors: Gül
authors: G
authors: Bekçioğlu-Neff
authors: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám 2, 16610, Prague 6, Czech Republic.
authors: Christoph
authors: C
authors: Allolio
authors: Department of Biobased Materials, Maastricht University, P.O. Box 616, 6200MD, Maastricht, The Netherlands.|Wavin Technology and Innovation, P.O. Box 173, 8000, AD Zwolle, The Netherlands.
authors: Yogesh S
authors: YS
authors: Desmukh
authors: Institut für Physikalische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, Münster, Germany.
authors: Michael Ryan
authors: MR
authors: Hansen
authors: Institut für Chemie, Martin-Luther-Universität Halle-Wittenberg, Von-Danckelmann-Platz 4, 06120, Halle (Saale), Germany. daniel.sebastiani@chemie.uni-halle.de.
authors: Daniel
authors: D
authors: Sebastiani
keywords: Hofmeister series; NMR spectroscopy; hydrogen bonds; ion pairs; molecular dynamics