Simple DFT Scheme for Estimating Negative Electron Affinities

Vibert, Christopher P.; Tozer, David J.

Abstract

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.

Citation

Vibert, C. P., & Tozer, D. J. (2018). Simple DFT Scheme for Estimating Negative Electron Affinities. Journal of Chemical Theory and Computation, 15(1), 241-248. https://doi.org/10.1021/acs.jctc.8b00938

• 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
• DOI: https://doi.org/10.1021/acs.jctc.8b00938