The melting point of lithium: an orbital-free first-principles molecular dynamics study

The melting point of liquid lithium near zero pressure is studied with large-scale orbital-free first-principles molecular dynamics (OF-FPMD) in the isobaric-isothermal ensemble. We adopt the Wang-Govind-Carter (WGC) functional as our kinetic energy density functional (KEDF) and construct a bulk-derived local pseudopotential (BLPS) for Li. Our simulations employ both the ‘heat-until-melts’ method and the coexistence method. We predict 465 K as an upper bound of the melting point of Li from the ‘heat-until-melts’ method, while we predict 434 K as the melting point of Li from the coexistence method. These values compare well with an experimental melting point of 453 K at zero pressure. Furthermore, we calculate a few important properties of liquid Li including the diffusion coefficients, pair distribution functions, static structure factors, and compressibilities of Li at 470 K and 725 K in the canonical ensemble. Our theoretically-obtained results show good agreement with known experimental results, suggesting that OF-FPMD using a non-local KEDF and a BLPS is capable of accurately describing liquid metals.

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