Dielectron Clathrate Hydrates with Unique Superexchange Spin Couplings

Clathrate hydrates have exhibited prospective applications not only in energy and environmental fields but also in icy magnetic materials because of the possibility of inclusion of radical species and their unique structures. In particular, the existence of dielectron clathrate hydrates has been experimentally reported. However, their structures and electronic or spintronic properties have not been explored yet. Here, we investigate four kinds of dielectron clathrate hydrates ((H2O)n2–, n = 36, 44, 48, and 52) and their spintronic properties using the density functional theory method and find that all dielectron hydrates feature stable bipolarons in icy surroundings with internal or H-bonding network permeating state electron distributions. The dielectron presents significant antiferromagnetic or ferromagnetic spin couplings through a novel electron-permeating H-bonding network superexchange mechanism. This work opens up the possibility of exploring novel icy crystal magnetic materials based on the clathr...