Explicitly correlated double hybrid DFT: a comprehensive analysis of the basis set convergence on the GMTKN55 database

Abstract

Double-hybrid density functional theory (DHDFT) offers a pathway to accuracies approaching composite wavefunction approaches like G4 theory. However, the GLPT2 (G{ö}rling 2nd order perturbation theory) term causes them to partially inherit the slow $\propto L^{-3}$ (with $L$ the maximum angular momentum) basis set convergence of correlated wavefunction methods. This could potentially be remedied by introducing F12 explicit correlation: we investigate the basis set convergence of both DHDFT and DHDFT-F12 for the large and chemically diverse GMTKN55 (general main-group thermochemistry, kinetics, and noncovalent interactions) benchmark suite. The B2GP-PLYP-D3(BJ) and revDSD-PBEP86-D4 double hybrid density functionals (DHDFs) are investigated as test cases, together with orbital basis sets as large as aug-cc-pV5Z and F12 basis sets as large as cc-pV(Q+d)Z-F12. We show that F12 greatly accelerates basis set convergence of DHDFs, to the point that even the modest cc-pVDZ-F12 basis set is closer to the basis set limit than cc-pV(Q+d)Z or def2-QZVPP in orbital-based approaches, and in fact comparable in quality to cc-pV(5+d)Z. Somewhat surprisingly, aug-cc-pVDZ-F12 is not required even for the anionic subsets. In conclusion, DHDF-F12/VDZ-F12 eliminates concerns about basis set convergence in both the development and application of double-hybrid functionals. Mass storage and I/O bottlenecks for larger systems can be circumvented by localized pair natural orbital approximations, which also exhibit much gentler system size scaling.

published version in JCTC: Open Access with Creative Commons license

References in corpus (6)

• Comment on: "Estimating the Hartree-Fock limit from finite basis set calculations" [Jensen F (2005) Theor Chem Acc 113:267]
• The cc-pV5Z-F12 basis set: reaching the basis set limit in explicitly correlated calculations
• The aug-cc-pVnZ-F12 Basis Set Family: Correlation Consistent Basis Sets for Explicitly Correlated Benchmark Calculations on Anions and Noncovalent Complexes
• Surprisingly Good Performance of XYG3 Family Functionals Using Scaled KS-MP3 Correlation
• Reduced-scaling double hybrid DFT with rapid basis set convergence through localized pair natural orbital F12
• Does GLPT2 Offer Any Actual Benefit Over Conventional HF-MP2 In the Context of Double-Hybrid Density Functionals?

Cited by in corpus (3)

• A double-hybrid density functional based on good local physics with outstanding performance on the GMTKN55 database
• Reduced-scaling double hybrid DFT with rapid basis set convergence through localized pair natural orbital F12
• Is explicitly correlated double hybrid DFT advantageous for vibrational frequencies?