The Sodium Anion Is Strongly Perturbed in the Condensed Phase even though It Appears like a Free Ion in Nuclear Magnetic Resonance Experiments

Solvated sodium anions (Na^-) were thought to behave essentially like isolated gas-phase ions that interact only weakly with their environments. For example, ²³Na NMR signals for solvated Na^- are very sharp, despite the potential for strong quadrupolar broadening. The sharp NMR signals appear to indicate a nearly spherical electron density of the ion. For the present study, ab initio molecular dynamics simulations and quadrupolar relaxation rate calculations were carried out for the Na^-/Na⁺ [2.2.2]cryptand system solvated in methylamine, followed by detailed analyses of the electric field gradient at the sodium nuclei. It is found that Na^- does not behave like a quasi-free ion interacting only weakly with its environment. Rather, the filled 3s shell of Na^- interacts weakly with the ion's own core and the nucleus, causing Na^- to appear in NMR experiments like a free ion.