Theoretical Investigation of Solvated Electron Chemistry in Molten CaCl2

Abstract

We used ab initio molecular dynamics calculations to examine a solution of Ca in molten CaCl₂. The dissolved Ca atoms ionize spontaneously and form solvated electrons whose state varies in time to form a polaron (one solvated electron) or a bipolaron (a pair of solvated electrons) or be in a delocalized state. We examined the reaction of solvated electrons with gaseous H₂, CH₄, CO₂, and N₂. The solvated electrons reduce H₂ to 2H^–, CH₄ to CH^3– + H^–, CO₂ to ${\mathrm{CO}}_2^{2-}$, and N₂ to 2N^3–, which could be intermediates in further reactions.