A density functional theory with correct long-range asymptotic behavior

TL;DR

This paper develops a new density functional theory approximation that accurately captures long-range interactions, improving predictions for atomic and molecular properties, including bonds, affinities, and polarizabilities.

Contribution

It introduces an exact exchange-correlation energy representation leading to a simple approximation with correct long-range behavior, combining local and explicit long-range exchange.

Findings

Accurately describes chemical bonds and bound anions

Provides reasonable affinity energies and polarizability predictions

Passes stringent tests like ionization potential ratios and charge quantization

Abstract

We derive an exact representation of the exchange-correlation energy within density functional theory (DFT) which spawns a class of approximations leading to correct long-range asymptotic behavior. In what amounts to be the simplest approximation, we obtain an electronic structure theory that combines a new local correlation en-ergy (based on Monte-Carlo calculations applied to the homogeneous electron gas (HEG)) and a combination of local and explicit long-ranged exchange. The theory is applied to several 1st row atoms and diatomic molecules where encouraging results are obtained: a good description of the chemical bond at the same time allowing for bound anions, reasonably accurate affinity energies and correct polarizability of an elongated hydrogen chain. Further stringent tests of DFT are passed: the ratio of ionization potential and highest orbital energy is close to unity and the atomic charge of two distant hydrogen atoms under large bias is quantized (integer).