A Comprehensive Assessment of the Effectiveness of Orbital Optimization in Double-Hybrid Density Functionals in the Treatment of Thermochemistry, Kinetics, and Noncovalent Interactions

The Journal of Physical Chemistry. a
Asim Najibi, Lars Goerigk

Abstract

Orbital optimization (OO) has been suggested as a way to solve some shortcomings of second-order Møller-Plesset (MP2) variants and double-hybrid density functionals (DHDFs). A closer inspection of the literature, however, shows that the only two studies on OO-DHDFs were limited to three nonempirical PBE-based functionals, which are known to be of only mediocre accuracy. Herein, we provide a more in-depth analysis of OO-DHDFs with the main focus being on main-group thermochemistry, kinetics, and noncovalent interactions. We reanalyze two PBE-based OO-DHDFs and present four new OO-DHDF variants, two of which make use of the spin-component-scaling idea in their nonlocal correlation part. We also provide a more thorough analysis of three OO-MP2 variants. After assessing more than 621 reference points, we come to the conclusion that the benefits of OO are not as straightforward as previously thought. Results heavily depend on the underlying parent method. While OO-SCS/SOS-MP2 usually provide improved results-including for noncovalently bound systems-the opposite is true for OO-MP2. OO-DHDFs, like their nonoptimized counterparts, still require London-dispersion corrections. Among the DHDFs, the largest effect of OO on thermochemical ...Continue Reading

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Citations

Aug 1, 2018·Physical Chemistry Chemical Physics : PCCP·Nisha MehtaLars Goerigk
Apr 17, 2020·Journal of Computational Chemistry·Arno Förster, Lucas Visscher
Apr 23, 2020·Journal of Chemical Theory and Computation·Alberto FabrizioClemence Corminboeuf
Aug 22, 2020·Journal of Chemical Theory and Computation·Zack M WilliamsFrederick R Manby

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