Comparison of the structures and electronic properties of sodalites containing alkali metals and alkali-earth metals and their hydrates

<p>The effects of different alkali and alkali-earth metal ions on the electronic structures and properties of sodalite M<sub><i>n</i></sub>[AlSiO<sub>4</sub>]<sub>6</sub> (M-SOD) and their hydrates M<sub><i>n</i></sub>[AlSiO<sub>4</sub>]<sub>6</sub>⋅8H<sub>2</sub>O (M=Li, Na, K, <i>n</i> = 6; M=Ca, <i>n</i> = 3) were studied using density functional theory method. Theoretical calculations predicted that the Al–O–Si bond angle and cation-framework oxide distance in sodalites with alkali metal cations are correlated with cell volumes. The reduced bandwidths in M-SOD (M=Li, Na and K) show that the inter-atomic orbital overlap in sodalites is weaker than those in the hydrate phases. Frontier molecular orbital analysis indicated that oxygen atoms in the frameworks and most metal ions of SOD and their corresponding hydrates exhibit high reactivity. The interactions existing in sodalites and hydrates were qualitative described. The calculated combination energies of metal ions with framework of sodalites are in the order of K<sup>+</sup>< Na<sup>+</sup>< Li<sup>+</sup>< Ca<sup>2+</sup>. This finding confirms the experimental observation for ion exchange.</p>