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      A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions

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          Abstract

          We present the updated and extended GMTKN55 benchmark database for more accurate and extensive energetic evaluation of density functionals and other electronic structure methods with detailed guidelines for method users.

          Abstract

          We present the GMTKN55 benchmark database for general main group thermochemistry, kinetics and noncovalent interactions. Compared to its popular predecessor GMTKN30 [Goerigk and Grimme J. Chem. Theory Comput., 2011, 7, 291], it allows assessment across a larger variety of chemical problems—with 13 new benchmark sets being presented for the first time—and it also provides reference values of significantly higher quality for most sets. GMTKN55 comprises 1505 relative energies based on 2462 single-point calculations and it is accessible to the user community via a dedicated website. Herein, we demonstrate the importance of better reference values, and we re-emphasise the need for London-dispersion corrections in density functional theory (DFT) treatments of thermochemical problems, including Minnesota methods. We assessed 217 variations of dispersion-corrected and -uncorrected density functional approximations, and carried out a detailed analysis of 83 of them to identify robust and reliable approaches. Double-hybrid functionals are the most reliable approaches for thermochemistry and noncovalent interactions, and they should be used whenever technically feasible. These are, in particular, DSD-BLYP-D3(BJ), DSD-PBEP86-D3(BJ), and B2GPPLYP-D3(BJ). The best hybrids are ωB97X-V, M052X-D3(0), and ωB97X-D3, but we also recommend PW6B95-D3(BJ) as the best conventional global hybrid. At the meta-generalised-gradient (meta-GGA) level, the SCAN-D3(BJ) method can be recommended. Other meta-GGAs are outperformed by the GGA functionals revPBE-D3(BJ), B97-D3(BJ), and OLYP-D3(BJ). We note that many popular methods, such as B3LYP, are not part of our recommendations. In fact, with our results we hope to inspire a change in the user community's perception of common DFT methods. We also encourage method developers to use GMTKN55 for cross-validation studies of new methodologies.

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          • Record: found
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          Generalized Gradient Approximation Made Simple

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            • Record: found
            • Abstract: not found
            • Article: not found

            Toward reliable density functional methods without adjustable parameters: The PBE0 model

              Bookmark
              • Record: found
              • Abstract: not found
              • Article: not found

              A new mixing of Hartree–Fock and local density-functional theories

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                Author and article information

                Journal
                PPCPFQ
                Physical Chemistry Chemical Physics
                Phys. Chem. Chem. Phys.
                Royal Society of Chemistry (RSC)
                1463-9076
                1463-9084
                2017
                2017
                : 19
                : 48
                : 32184-32215
                Affiliations
                [1 ]School of Chemistry
                [2 ]The University of Melbourne
                [3 ]Parkville
                [4 ]Australia
                [5 ]Universität Bonn
                [6 ]Mulliken Center for Theoretical Chemistry
                [7 ]Bonn
                [8 ]Germany
                Article
                10.1039/C7CP04913G
                29110012
                878bdf20-b108-492a-8ade-60a2bb441464
                © 2017

                http://creativecommons.org/licenses/by-nc/3.0/

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