Simple quantitative estimate of the derivative discontinuity of the exchange-correlation functional in atoms and molecules

2006/11/18 by F. P. Rosselli, Rosselli, F. P., Albérico B. F. da Silva +3
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Advanced Physical and Chemical Molecular Interactions #Atomic Physics (physics.atom-ph) #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Materials Science (cond-mat.mtrl-sci) #Spectroscopy and Quantum Chemical Studies

paper · pdf · doi:10.48550/arxiv.physics/0611180

openalex publication_date 2006/11/18 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

Abstract

The derivative discontinuity of the exchange-correlation functional of density-functional theory is cast as the difference of two types of electron affinities. We show that standard Kohn-Sham calculations can be used to calculate both affinities, and that their difference benefits from substantial and systematic error cancellations, permitting reliable estimates of the derivative discontinuity. Numerical calculations for atoms and molecules show that the discontinuity is quite large (typically several eV), and significantly and consistently improves the agreement of the calculated fundamental energy gap with the experimental gaps. The percentage error of the single-particle gap is reduced in favorable cases by more than one order of magnitude, and even in unfavorable cases by about a factor of two.

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