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Density functionals with full nonlocal exchange, nonlocal rung‐3.5 correlation, and D3 dispersion: Combined accuracy for general main‐group thermochemistry, kinetics, and noncovalent interactions
Author(s) -
Ramos Chloe,
Muehlbrad Jeremiah,
Janesko Benjamin G.
Publication year - 2021
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26728
Subject(s) - thermochemistry , dispersion (optics) , absolute deviation , chemistry , statistical physics , correlation , physics , dispersion relation , thermodynamics , quantum mechanics , mathematics , statistics , geometry
We introduce the HF‐R35‐D3(BJ) functional combining full nonlocal exact (Hartree‐Fock‐like, HF) exchange, inexpensive rung‐3.5 correlation constructed from nonlocal one‐electron operators, and nonlocal D3 dispersion corrections. HF‐R35‐D3(BJ) is among the first full‐exact‐exchange functionals offering competitive accuracy for general main‐group thermochemistry, kinetics, and noncovalent interactions. HF‐R35‐D3(BJ) gives weighted mean absolute deviation WTMAD‐2 8.5 kcal/mol across the entire GMTKN55 dataset, outperforming most dispersion‐corrected semilocal functionals and approaching the accuracy of dispersion‐corrected global hybrids. This requires six fitted parameters, three each in the nonlocal correlation and dispersion corrections. Full nonlocal exchange appears to help give accurate binding energies and reasonable energy orderings for water hexamers. These results motivate continued exploration of inexpensive nonlocal correlation corrections to nonlocal exchange.