1. Dynamical Dimension to the Hofmeister Series: Insights from First-Principles Simulations
- Author
-
Yogesh S. Desmukh, Michael Ryan Hansen, Gül Bekçioğlu-Neff, Christoph Allolio, and Daniel Sebastiani
- Subjects
LIQUID WATER ,Kosmotropic ,Hofmeister series ,010402 general chemistry ,01 natural sciences ,NMR CHEMICAL-SHIFTS ,DENSITY-FUNCTIONAL THEORY ,PRINCIPLES MOLECULAR-DYNAMICS ,Molecular dynamics ,NMR spectroscopy ,X-RAY-DIFFRACTION ,WATER-MOLECULES ,Computational chemistry ,1ST PRINCIPLES ,AQUEOUS-SOLUTIONS ,0103 physical sciences ,Physical and Theoretical Chemistry ,HYDROGEN-BOND STRUCTURE ,ion pairs ,Aqueous solution ,010304 chemical physics ,Hydrogen bond ,Chemistry ,Chemical shift ,METAL-ION ,molecular dynamics ,Atomic and Molecular Physics, and Optics ,0104 chemical sciences ,Chaotropic agent ,Chemical physics ,hydrogen bonds ,Proton NMR - 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 (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.
- Published
- 2015