Rational Design of Superconducting Metal Hydrides via Chemical Pressure Tuning**

The high critical superconducting temperatures (T_cs) of metal hydride phases with clathrate-like hydrogen networks have generated great interest. Herein, we employ the Density Functional Theory-Chemical Pressure (DFT-CP) method to explain why certain electropositive elements adopt these structure types, whereas others distort the hydrogenic lattice, thereby decreasing the T_c. The progressive opening of the H₂₄ polyhedra in MH₆ phases is shown to arise from internal pressures exerted by large metal atoms, some of which may favor an even higher hydrogen content that loosens the metal atom coordination environments. The stability of the LaH₁₀ and LaBH₈ phases is tied to stuffing of their shared hydrogen network with either additional hydrogen or boron atoms. The predictive capabilities of DFT-CP are finally applied to the Y−X−H system to identify possible ternary additions yielding a superconducting phase stable to low pressures.