Density Functional Theory of Material Design$:$ Fundamentals and Applications$-II$

Abstract

This is the second and the final part of the review on density functional theory (DFT), referred to as DFT-II. In the first review, DFT-I, we have discussed wavefunction-based methods, their complexity, and the basic of density functional theory. In DFT-II, we focus on fundamentals of DFT and their implications for the betterment of the theory. We start our presentation with the exact DFT result followed by the concept of exchange-correlation (xc) or Fermi-Coulomb hole and its relation with xc energy functional. We also provide the exact conditions for the xc-hole, xc-energy and xc-potential along with their physical interpretation. Next, we describe the extension of DFT for non-integer numbers of electrons, the piecewise linearity of total energy and discontinuity of chemical potential at integer particle numbers, and derivative discontinuity of the xc potential, which has consequences on fundamental gap of solids. After that, we present how one obtain more accurate xc energy functionals by going beyond LDA. We discuss the gradient expansion approximation (GEA), generalized gradient approximation (GGA), and hybrid functional approaches to designing better xc energy functionals that give accurate total energies but fail to predict properties like the ionization potential and the band gap. Thus, we describe different methods of modeling these potentials and the results of their application for the calculation of the band gaps of different solids to highlight accuracy of different xc potential. Finally, we conclude with a glimpse on orbital-free density functional theory and the machine learning approach .