Collective water dynamics in the first solvation shell drive the NMR relaxation of aqueous quadrupolar cations

Abstract : Towards accurate solvation dynamics of divalent cations in water using the polarizable amoeba force field: From energetics to structure Solute size effects on the solvation structure and diffusion of ions in liquid methanol under normal and cold conditions Using molecular simulations, we analyze the microscopic processes driving the Nuclear Magnetic Resonance (NMR) relaxation of quadrupolar cations in water. The fluctuations of the Electric Field Gradient (EFG) experienced by alkaline and magnesium cations, which determine the NMR relaxation time, are mainly due to the dynamics of water molecules in their solvation shell. The dynamics of the ion plays a less important role, with the exception of the short-time dynamics in the lighter Li + case, for which rattling in the solvent cage results in oscillations of the EFG autocorrelation function (ACF). Several microscopic mechanisms that may a priori contribute to the decay of the EFG-ACF occur in fact over too long time scales: entrance/exit of individual water molecules into/from the solvation shell, rotation of a molecule around the ion, or reorientation of the molecule. In contrast, the fluctuations of the ion-water distance are clearly correlated to that of the EFG. Nevertheless, it is not sufficient to consider a single molecule due to the cancellations arising from the symmetry of the solvation shell. The decay of the EFG-ACF, hence NMR relaxation, is in fact governed by the collective symmetry-breaking fluctuations of water in the first solvation shell.
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Antoine Carof, Mathieu Salanne, Thibault Charpentier, Benjamin Rotenberg. Collective water dynamics in the first solvation shell drive the NMR relaxation of aqueous quadrupolar cations. Journal of Chemical Physics, American Institute of Physics, 2016, 145, pp.124508. ⟨http://scitation.aip.org/content/aip/journal/jcp/145/12/10.1063/1.4963682⟩. ⟨10.1063/1.4963682⟩. ⟨cea-01374228⟩

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