Dynamical Dimension to the Hofmeister Series: Insights from First-Principles Simulations

0461204 - ÚOCHB 2017 RIV DE eng J - Journal Article
Bekcioglu-Neff, G. - Allolio, Christoph - Desmukh, Y. S. - Hansen, M. R. - Sebastiani, D.
Dynamical Dimension to the Hofmeister Series: Insights from First-Principles Simulations.
ChemPhysChem. Roč. 17, č. 8 (2016), s. 1166-1173. ISSN 1439-4235. E-ISSN 1439-7641
Institutional support: RVO:61388963
Keywords : Hofmeister series * hydrogen bonds * ion pairs * molecular dynamics * NMR spectroscopy
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 3.075, year: 2016

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 (HNMR)-H-1 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.
Permanent Link: http://hdl.handle.net/11104/0260871