CHEM In the literature: partially resolved

A practical functional that obeys the flat-plane condition

In plain words

The exact energy changes in straight lines when a fraction of an electron is added or when spin is fractionally shared, and approximate functionals bend those lines. Bending one way spreads electrons out too much; bending the other way mistreats stretched bonds.

Precise statement

Construct an exchange-correlation approximation, at cost no higher than a global hybrid, whose energy $E(N, S_z)$ is piecewise linear in fractional electron number N (no delocalization error) and constant in fractional spin at fixed N (no static correlation error), as tested on H2+ and H2 dissociation, fractional-charge atoms and the stretched-bond benchmark sets, while keeping main-group thermochemistry errors below 3 kcal/mol. An answer is such a functional, or a proof that no functional of a given class can satisfy both conditions.

What would settle it

A functional passing fractional-charge, fractional-spin and standard thermochemistry benchmarks simultaneously, or a no-go theorem for a defined functional class.

Status in the literature

In 2021 the DM21 learned functional, trained on fractional-charge and fractional-spin data, reduced both errors for small systems; no functional satisfies both conditions in general.

See also