Origin of the step structure of molecular exchange–correlation potentials

Abstract

The exact exchange–correlation potential of a stretched heteronuclear diatomic molecule exhibits a localized upshift in the region around the more electronegative atom; by this device the Kohn–Sham scheme ensures that the molecule dissociates into neutral atoms. Baerends and co-workers showed earlier that the upshift originates in the response part of the exchange–correlation potential. We describe a reliable numerical method for constructing the response potential of a given many-electron system and report accurate plots of this quantity. We also demonstrate that the step feature itself can be obtained directly from the interacting wavefunction of the system by computing the so-called average local electron energy. These findings illustrate in previously unavailable detail the mechanism of the formation of the upshift and the role played by static correlation in this process.