Basis Set Requirements of σ‑Functionals for Gaussian- and Slater-Type Basis Functions and Comparison with Range-Separated Hybrid and Double Hybrid Functionals

• Published in: Journal of chemical theory and computation 2024-03, Vol.20 (6), p.2404-2422
• Main Authors: Fauser, Steffen, Förster, Arno, Redeker, Leon, Neiss, Christian, Erhard, Jannis, Trushin, Egor, Görling, Andreas
• Format: Article
• Language: English
• Subjects: Accuracy; Basis functions; Computational efficiency; Functionals; Mathematical analysis; Physical properties; Quantum Electronic Structure
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.3c01132

σ-Functionals belong to the class of Kohn–Sham (KS) correlation functionals based on the adiabatic-connection fluctuation–dissipation theorem and are technically closely related to the random phase approximation (RPA). They have the same computational demand as the latter, with the computational effort of an energy evaluation for both methods being lower than that of a preceding hybrid DFT calculation for typical systems but yield much higher accuracy, reaching chemical accuracy of 1 kcal/mol for quantities such as reactions and transition energies in main group chemistry. In previous work on σ-functionals, rather large Gaussian basis sets have been used. Here, we investigate the actual basis set requirements of σ-functionals and present three setups that employ smaller Gaussian basis sets ranging from quadruple-ζ (QZ) to triple-ζ (TZ) quality and represent a good compromise between accuracy and computational efficiency. Furthermore, we introduce an implementation of σ-functionals based on Slater-type basis sets and present two setups of QZ and TZ quality for this implementation. We test the accuracy of these setups on a large database of various physical properties and types of reactions, as well as equilibrium geometries and vibrational frequencies. As expected, the accuracy of σ-functional calculations becomes somewhat lower with a decreasing basis set size. However, for all setups considered here, calculations with σ-functionals are clearly more accurate than those within the RPA and even more so than those of the conventional KS methods. For the smallest setup using Gaussian-type basis functions and Slater-type basis functions, we introduce a reparametrization that reduces the loss in accuracy due to the basis set error to some extent. A comparison with the range-separated hybrid ωB97X-V and the double hybrid DSD-BLYP-D3 shows that σ functionals outperform in accuracy both of these accurate and, for their class, representative functionals.