An ab initio study of the stability and electronic structure of univalent magnesium salts

Large basis and well-correlated ab initio electronic structure calculations have been performed on the simple Mg(I) salts, Mg₂F₂ and Mg₂Cl₂. The electron withdrawing power of the halogens gives rise to significant metal-metal bonding and consequently these as yet unobserved, univalent salts are calculated to be 10–12 kcal more stable than if the second magnesium atom were absent from the molecule. With this stability, these species provide an energetically more accessible Mg atom for subsequent reaction than does solid magnesium where the atomization energy is 35 kcal. Thus, formal univalency of magnesium affords a route to activated magnesium.