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Simple DFT Scheme for Estimating Negative Electron Affinities

Vibert, Christopher P.; Tozer, David J.

Simple DFT Scheme for Estimating Negative Electron Affinities Thumbnail


Christopher P. Vibert


A simple density functional theory (DFT) scheme is proposed for estimating negative vertical electron affinities of neutral systems, based on a consideration of the integer discontinuity and density scaling homogeneity. The key feature is the derivation of two system-dependent exchange-correlation functionals, one appropriate for the electron deficient side of the integer and one appropriate for the electron abundant side. The electron affinity is evaluated as a linear combination of frontier orbital energies from self-consistent Kohn–Sham calculations on the neutral system using these functionals. For two assessments comprising a total of 43 molecules, the scheme provides electron affinities that are in good agreement with experimental values and which are an improvement over those from the DFT method of Tozer and De Proft [ J. Phys. Chem. A 2005, 109, 8923]. The scheme is trivial to implement in any Kohn–Sham program, and the computational cost is that of a series of generalized gradient approximation Kohn–Sham calculations. More generally, the study provides a prescription for performing low-cost, self-consistent Kohn–Sham calculations that yield frontier orbital energies that approximately satisfy the appropriate Koopmans conditions, without the need for exact exchange.

Journal Article Type Article
Acceptance Date Nov 29, 2018
Online Publication Date Nov 29, 2018
Publication Date Nov 29, 2018
Deposit Date Jan 21, 2019
Publicly Available Date Nov 29, 2019
Journal Journal of Chemical Theory and Computation
Print ISSN 1549-9618
Electronic ISSN 1549-9626
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 15
Issue 1
Pages 241-248
Public URL


Accepted Journal Article (381 Kb)

Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of chemical theory and computation copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see

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