First principles local pseudopotential for silver: towards orbital-free density-functional theory for transition metals.
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 (T(TF)) and von Weizsacker (T(vW)) functionals (T(vW)+0.4T(TF)) 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.
Zhou
Baojing
B
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
Carter
Emily A
EA
D002627:Chemistry, Physical / Q000379:methods*; D004396:Coloring Agents; D003460:Crystallization; D008956:Models, Chemical; D015233:Models, Statistical; D008962:Models, Theoretical; D010825:Physics / Q000379:methods; D012834:Silver / Q000737:chemistry*; D012984:Software; D013194:Staining and Labeling; D028561:Transition Elements / Q000737:chemistry*
D004396:Coloring Agents; D028561:Transition Elements; D012834:Silver