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The X₂MH₆ family, consisting of an electropositive cation X and a main group metal M octahedrally coordinated by hydrogen, has been predicted to hold promise for high-temperature conventional superconductivity. Herein, we analyze the electronic structure of two members of this family, Mg₂IrH₆ and Ca₂IrH₆, showing why the former may possess superconducting properties rivaling those of the cuprates, whereas the latter does not. Within Mg₂IrH₆ the vibrations of the IrH₆^4- anions are key for the superconducting mechanism, and they induce coupling in the eg^* set, which are antibonding between the H 1s and the Ir dₗℂ-ₘℂ or dₙℂ orbitals. Because calcium possesses low-lying d-orbitals, eg^* Ca d back-donation is preferred, quenching the superconductivity. Our analysis explains why high critical temperatures were only predicted for second or third row X metal atoms, and may hold implications for superconductivity in other systems where the antibonding anionic states are filled.
Wang et al. (Mon,) studied this question.