Ion Hydration and Ion Pairing as Probed by THz Spectroscopy
Dr. Gerhard Schwaab
Lehrstuhl für Physikalische Chemie II, Ruhr-Universität Bochum, 44780 Bochum, Germany
Search for more papers by this authorDr. Federico Sebastiani
Lehrstuhl für Physikalische Chemie II, Ruhr-Universität Bochum, 44780 Bochum, Germany
Search for more papers by this authorCorresponding Author
Prof. Martina Havenith
Lehrstuhl für Physikalische Chemie II, Ruhr-Universität Bochum, 44780 Bochum, Germany
Search for more papers by this authorDr. Gerhard Schwaab
Lehrstuhl für Physikalische Chemie II, Ruhr-Universität Bochum, 44780 Bochum, Germany
Search for more papers by this authorDr. Federico Sebastiani
Lehrstuhl für Physikalische Chemie II, Ruhr-Universität Bochum, 44780 Bochum, Germany
Search for more papers by this authorCorresponding Author
Prof. Martina Havenith
Lehrstuhl für Physikalische Chemie II, Ruhr-Universität Bochum, 44780 Bochum, Germany
Search for more papers by this authorGraphical Abstract
Testing the water: The microscopic interplay between cations, anions, and water can be understood by THz-FTIR spectroscopy. Dissection of the spectra shows that the full response of the solvating water when dissolving salts can not be explained from the individual properties (such as the ion radius, the ion–water interaction, the structural hydration shell size, etc.) alone; cooperativity effects need to be included.
Abstract
Ion hydration is of pivotal importance for many fundamental processes. Various spectroscopic methods are used to study the retardation of the hydration bond dynamics in the vicinity of anions and cations. Here we introduce THz-FTIR spectroscopy as a powerful method to answer the open questions. We show through dissection of THz spectra that we can pinpoint characteristic absorption features that can be attributed to the rattling modes of strongly hydrating ions within their hydration cages as well as vibrationally induced charge fluctuations in the case of weakly hydrating ions. Further analysis yields information on anion–cation cooperativity, the size of the dynamic hydration shell, as well as the lifetimes of these collective ion-hydration water modes and their connecting thermal bath states. Our study provides evidence for a non-additive behavior, thus questioning the simplified Hofmeister model. THz spectroscopy enables ion pairing to be observed and quantified at a high salt concentration.
Conflict of interest
The authors declare no conflict of interest.
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