Asymptotic Behavior of the Exchange-Correlation Energy Density and the Kohn-Sham Potential in Density Functional Theory: Exact Results and Strategy for Approximations
2019-10-01T16:00:15Z (GMT) by
The present work is a review of two analytical properties of the exact exchange-correlation (xc) functional in density-functional theory. These properties are the asymptotic behavior of the xc energy density per particle and the asymptotic behavior of the Kohn-Sham potential, in finite many-electron systems. The derivation of the asymptotic forms for both quantities is reviewed, employing the concepts of the adiabatic connection and of the xc hole with relation to the first quantity and the electron exact factorization approach for the second one. Furthermore, it is shown that the correct asymptotic behavior of one of the aforementioned quantities does not guarantee a correct behavior of the other. In this process, a new quantity, the xc hole response function, is defined and its exact exchange part is analytically derived. The extent to which existing xc approximations satisfy the named exact properties is reviewed and the relationship between correct asymptotics and freedom from one-electron self-interaction in DFT is discussed. Finally, a strategy for development of advanced approximations for exchange and correlation with a correct asymptotic behavior is suggested.