A density functional theory with correct long-range asymptotic behavior

摘要

We derive an exact representation of the exchange-correlation energy withindensity functional theory (DFT) which spawns a class of approximations leadingto correct long-range asymptotic behavior. In what amounts to be the simplestapproximation, we obtain an electronic structure theory that combines a newlocal correlation en-ergy (based on Monte-Carlo calculations applied to thehomogeneous electron gas (HEG)) and a combination of local and explicitlong-ranged exchange. The theory is applied to several 1st row atoms anddiatomic molecules where encouraging results are obtained: a good descriptionof the chemical bond at the same time allowing for bound anions, reasonablyaccurate affinity energies and correct polarizability of an elongated hydrogenchain. Further stringent tests of DFT are passed: the ratio of ionizationpotential and highest orbital energy is close to unity and the atomic charge oftwo distant hydrogen atoms under large bias is quantized (integer).