Orbital-free density-functional theory (OF-DFT) with modern kinetic-energy density functionals (KEDFs) is a linear scaling technique that accurately describes nearly-free-electron-like (main group) metals. In an attempt towards extending OF-DFT to transition metals, here we consider whether OF-DFT can be used effectively to study Ag, a metal with a localized d shell. OF-DFT has two approximations: use of a KEDF and local pseudopotentials (LPSs). This paper reports construction of a reasonably accurate LPS for Ag by means of inversion of the Kohn-Sham (KS) DFT equations in a bulk crystal environment. The accuracy of this LPS is determined within KS-DFT (where the exact noninteracting kinetic energy is employed) by comparing its predictions of bulk properties to those obtained from a conventional (orbital-based) nonlocal pseudopotential (NLPS). We find that the static bulk properties of fcc and hcp Ag predicted within KS-DFT using this LPS compare fairly well to those predicted by an NLPS. With the transferability of the LPS established, we then use this LPS in OF-DFT, where several approximate KEDFs were tested. We find that a combination of the Thomas-Fermi (TTF) and von Weizsäcker (TvW) functionals (TvW +0.4 TTF) produces better densities than those from the linear-response-based Wang-Teter KEDF. However, the equations of state obtained from both KEDFs in OF-DFT contain unacceptably large errors. The lack of accurate KEDFs remains the final barrier to extending OF-DFT to treat transition metals.
All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry