English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools annual

Global: Zendy Free Plan

Global: Zendy Tools monthly

Global: Zendy Plus monthly

Double-hybrid density functional theory (DHDFT) offers a pathway toaccuracies approaching composite wavefunction approaches like G4 theory.However, the GLPT2 (G{\"o}rling 2nd order perturbation theory) term causes themto partially inherit the slow $\propto L^{-3}$ (with $L$ the maximum angularmomentum) basis set convergence of correlated wavefunction methods. This couldpotentially be remedied by introducing F12 explicit correlation: we investigatethe basis set convergence of both DHDFT and DHDFT-F12 for the large andchemically diverse GMTKN55 (general main-group thermochemistry, kinetics, andnoncovalent interactions) benchmark suite. The B2GP-PLYP-D3(BJ) andrevDSD-PBEP86-D4 double hybrid density functionals (DHDFs) are investigated astest cases, together with orbital basis sets as large as aug-cc-pV5Z and F12basis sets as large as cc-pV(Q+d)Z-F12. We show that F12 greatly acceleratesbasis set convergence of DHDFs, to the point that even the modest cc-pVDZ-F12basis set is closer to the basis set limit than cc-pV(Q+d)Z or def2-QZVPP inorbital-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 anionicsubsets. In conclusion, DHDF-F12/VDZ-F12 eliminates concerns about basis setconvergence in both the development and application of double-hybridfunctionals. Mass storage and I/O bottlenecks for larger systems can becircumvented by localized pair natural orbital approximations, which alsoexhibit much gentler system size scaling.

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