Compression and phase diagram of lithium hydrides at elevated pressures and temperatures by first-principles calculation

High pressure and high temperature properties of AB (A  =  6Li, 7Li; B  =  H, D, T) are comprehensively investigated with first-principles methods. It is found that H−sublattice features in the low-pressure electronic structure near the Fermi level of LiH are shifted to that dominated by the Li+ sublattice under compression. The lattice dynamics are studied in quasi-harmonic approximation, from which the phonon contribution to the free energy and the isotopic effects are accurately modelled with the aid of a parameterized double-Debye model. The equation of state (EOS) obtained matches perfectly with available static experimental data. The calculated principal Hugoniot is also in accordance with that derived from shock wave experiments. Using the calculated principal Hugoniot and the previous theoretical melting curve, we predict a shock melting point at 56 GPa and 1923 K. In order to establish the phase diagram for LiH, the phase boundaries between the B1 and B2 solid phases are explored. The B1–B2-liquid triple point is determined at about 241 GPa and 2413 K. The remarkable shift in the phase boundaries with isotopic effect and temperature reveal the significant role played by lattice vibrations. Furthermore, the Hugoniot of the static-dynamic coupling compression is assessed. Our EOS suggests that a precompression of the sample to 50 GPa will allow the shock Hugoniot to pass through the triple point and enter the B2 solid phase. This transition leads to a discontinuity with 4.6% volume collapse—about four times greater than the same B1–B2 transition at zero temperature.