Terahertz Spectra of Microsolvated Ions: Do They Reveal Bulk Solvation Properties?

Abstract

Complementing mid-infrared (mid-IR) spectroscopy mainly in the OH stretching region, liquid-state far-IR spectroscopy is successful in elucidating the properties of aqueous solutions by providing direct access to the hallmark of H-bonding at terahertz (THz) frequencies, namely, the H-bond network peak of water at roughly 200 cm^-1 and its modifications in the hydration shells around solutes. Here, the idea is scrutinized whether ion hydration can be understood by studying the THz regime of "small" ion-water clusters in the gas phase as a function of size with subsequent extrapolation to the bulk limit. Our ab initio simulations of Na⁺(H₂O) _n clusters followed by rigorous decomposition of their THz response demonstrate that the 200 cm^-1 network peak is suppressed even at n = 20 in the gas phase, yet it emerges when transferring ion-water complexes as small as n = 7 out of the liquid into vacuum. The underlying physical reason is not missing electronic polarization or charge-transfer effects in the gas phase, but rather the distinctly different structural dynamics of finite ion-water clusters in the gas phase compared to ion-water complexes of the same size in the liquid phase.