Short-Range Cooperative Slow-down of Water Solvation Dynamics Around SO₄ ^2--Mg²⁺ Ion Pairs

The presence of ions affects the structure and dynamics of water on a multitude of length and time scales. In this context, pairs of Mg²⁺ and SO₄ ^2- ions in water constitute a prototypical system for which conflicting pictures of hydration geometries and dynamics have been reported. Key issues are the molecular pair and solvation shell geometries, the spatial range of electric interactions, and their impact on solvation dynamics. Here, we introduce asymmetric SO₄ ^2- stretching vibrations as new and most specific local probes of solvation dynamics that allow to access ion hydration dynamics at the dilute concentration (0.2 M) of a native electrolyte environment. Highly sensitive heterodyne 2D-IR spectroscopy in the fingerprint region of the SO₄ ^2- ions around 1100 cm^-1 reveals a specific slow-down of solvation dynamics for hydrated MgSO₄ and for Na₂SO₄ in the presence of Mg²⁺ ions, which manifests as a retardation of spectral diffusion compared to aqueous Na₂SO₄ solutions in the absence of Mg²⁺ ions. Extensive molecular dynamics and density functional theory QM/MM simulations provide a microscopic view of the observed ultrafast dephasing and hydration dynamics. They suggest a molecular picture where the slow-down of hydration dynamics arises from the structural peculiarities of solvent-shared SO₄ ^2--Mg²⁺ ion pairs.