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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.

Based upon precise terahertz (THz) measurements of the solvated amino acid glycine and accompanying ab‐initio molecular‐dynamics simulations, we show that the N‐C‐C‐O open/close mode at 315 cm−1 serves as a sensitive, label‐free probe for the local protonation of the amide group. Experimentally, we can show that this holds not only for glycine but also for diglycine and valine. The approach is more general, since the changes due to protonation result in intensity changes which can be probed by THz time domain (0–50 cm−1) as well as by precise THz‐FT spectroscopy (50–400 cm−1). A detailed analysis allows us to directly correlate the titration spectra with pK a values. This demonstrates the potential of THz spectroscopy to probe the charge state of a natural amino acid in water in a label‐free manner., Based upon precise terahertz (THz) measurements of the solvated amino acid glycine and accompanying ab‐initio molecular‐dynamics simulations, it is shown that the N‐C‐C‐O open/close mode at 315 cm−1 serves as a sensitive, label‐free probe for the local protonation of the amide group.

Many phenomena depend on CaCO3 nucleation where the role of water remains enigmatic. Changes in THz absorption during the early stages of CaCO3 nucleation evidence altered coupled motions of hydrated calcium and carbonate ions. The direct link between these changes and the continuous development of the ion activity product reveals the locus of a liquid–liquid binodal limit. The data strongly suggest that proto-structured amorphous CaCO3 forms through solidification of initially liquid precursors. Furthermore, polycarboxylates, which stabilize liquid precursors of CaCO3, significantly enhance the kinetic stability of the metastable liquid–liquid state, but they do not affect the locus of the binodal limit. The importance of water network dynamics in phase separation mechanisms can be understood based on the notions of the pre-nucleation cluster pathway, and is likely to be more general for aqueous systems. published