Effects of Nanoconfinement on Dynamics in Concentrated Aqueous Magnesium Chloride Solutions.

Water behavior in various natural and manufactured settings is influenced by confinement in organic or inorganic frameworks and the presence of solutes. Here, the effects on dynamics from both confinement and the addition of solutes are examined. Specifically, water and ion dynamics in concentrated (2.5-4.2 m) aqueous magnesium chloride solutions confined in mesoporous silica (2.8 nm pore diameter) were investigated using polarization selective pump-probe and 2D infrared spectroscopies. Fitting the rotational and spectral diffusion dynamics measured by the vibrational probe, selenocyanate, with a previously developed two-state model revealed distinct behaviors at the interior of the silica pores (core state) and near the wall of the confining framework (shell state). The shell dynamics are noticeably slower than the bulk, or core, dynamics. The concentration-dependent slowing of the dynamics aligns with behavior in the bulk solutions, but the spectrally separated water-associated and Mg-associated forms of the selenocyanate probe exhibit different responses to confinement. The disparity in the complete reorientation times is larger upon confinement, but the spectral diffusion dynamics become more similar near the silica surface. The length scales that characterize the transition from surface-influenced to bulk-like behavior for the salt solutions in the pores are discussed and compared to those of pure water and an organic solvent confined in the same pores. These comparisons offer insights into how confinement modulates the properties of different liquids.