Exploring Avenues Beyond Revised DSD Functionals: I. range separation, with xDSD as a special case

Abstract

We have explored the use of range separation as a possible avenue for further improvement on our revDSD minimally empirical double hybrid functionals. Such $\omega$DSD functionals encompass the XYG3 type of double hybrid (i.e., xDSD) as a special case for $\omega$->0. As in our previous studies, the large and chemically diverse GMTKN55 benchmark suite was used for evaluation. Especially when using the D4 rather than D3BJ dispersion model, xDSD has a slight performance advantage in WTMAD2. As found previously, PBEP86 is the winning combination for the semilocal parts. xDSDn-PBEP86-D4 marginally outperforms the previous 'best in class' $\omega$B97M(2) Berkeley double hybrid, but without range separation and using fewer than half the number of empirical parameters. Range separation turns out to offer only marginal further improvements on GMTKN55 itself. While $\omega$B97M(2) still yields better performance for small-molecule thermochemistry, this is outweighed in WTMAD2 by superior performance of the new functionals for conformer equilibria. Results for two external test sets with pronounced static correlation effects may indicate that range-separated double hybrids are more resilient to such effects.

arXiv commentJ. Phys. Chem. A 125, ASAP (2021) Creative Commons License (1st of two papers back-to-back)

References in corpus (14)

• W4 theory for computational thermochemistry: in pursuit of confident sub-kJ/mol predictions
• Long-range/short-range separation of the electron-electron interaction in density functional theory
• Van der Waals forces in density functional theory: perturbational long-range electron interaction corrections
• Solid-state optical absorption from optimally-tuned time-dependent range-separated hybrid density functional theory
• Empirical Double-Hybrid Density Functional Theory: A 'Third Way' In Between WFT and DFT
• SCAN-based hybrid and double-hybrid density functionals from models without fitted parameters
• Benchmark tests of a strongly constrained semilocal functional with a long-range dispersion correction
• Performance of ab initio and density functional methods for conformational equilibria of CnH2n+2 alkane isomers (n=2-8)
• Performance of Localized Coupled Cluster Methods in a Moderately Strong Correlation Regime: Hückel-Möbius Interconversions in Expanded Porphyrins
• Canonical and DLPNO-based G4(MP2)XK-inspired composite wavefunction methods parametrized against large and chemically diverse training sets: Are they more accurate and/or robust than double hybrid DFT?
• Some Observations on the Performance of the Most Recent Exchange-Correlation Functionals for the Large and Chemically Diverse GMTKN55 Benchmark
• Exploring Avenues Beyond Revised DSD Functionals: II. Random-Phase Approximation and scaled MP3 corrections
• Canonical and DLPNO-based composite wavefunction methods parametrized against large and chemically diverse training sets. 2. Correlation consistent basis sets, core-valence correlation, and F12 alternatives
• Comment on: Doubly hybrid density functional xDH-PBE0 from a parameter-free global hybrid model PBE0 (J. Chem. Phys. 136, 174103 (2012))

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