Exchange–Correlation Functionals via Local Interpolation along the Adiabatic Connection

Vuckovic, Stefan; Irons, Tom J.P.; Savin, Andreas; Teale, Andrew M.; Gori-Giorgi, Paola

Abstract

The construction of density-functional approximations is explored by modeling the adiabatic connection locally, using energy densities defined in terms of the electrostatic potential of the exchange−correlation hole. These local models are more amenable to the construction of size-consistent approximations than their global counterparts. In this work we use accurate input local ingredients to assess the accuracy of a range of local interpolation models against accurate exchange−correlation energy densities. The importance of the strictly correlated electrons (SCE) functional describing the strong coupling limit is emphasized, enabling the corresponding interpolated functionals to treat strong correlation effects. In addition to exploring the performance of such models numerically for the helium and beryllium isoelectronic series and the dissociation of the hydrogen molecule, an approximate analytic model is presented for the initial slope of the local adiabatic connection. Comparisons are made with approaches based on global models, and prospects for future approximations based on the local adiabatic connection are discussed.

Citation

Vuckovic, S., Irons, T. J., Savin, A., Teale, A. M., & Gori-Giorgi, P. (2016). Exchange–Correlation Functionals via Local Interpolation along the Adiabatic Connection. Journal of Chemical Theory and Computation, 12(6), 2598-2610. https://doi.org/10.1021/acs.jctc.6b00177

• Journal Article Type: Article
• Acceptance Date: Apr 26, 2016
• Online Publication Date: May 17, 2016
• Publication Date: Jun 14, 2016
• Deposit Date: May 27, 2016
• Publicly Available Date: May 27, 2016
• Journal: Journal of Chemical Theory and Computation
• Print ISSN: 1549-9618
• Electronic ISSN: 1549-9626
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 12
• Issue: 6
• Pages: 2598-2610
• DOI: https://doi.org/10.1021/acs.jctc.6b00177
• Public URL: https://nottingham-repository.worktribe.com/output/783748
• Publisher URL: http://pubs.acs.org/doi/abs/10.1021/acs.jctc.6b00177
• Contract Date: May 27, 2016