Benchmark tests of a strongly constrained semilocal functional with a long-range dispersion correction

Article

关键词: GENERALIZED GRADIENT APPROXIMATION;    MAIN-GROUP THERMOCHEMISTRY;    QUANTUM-CHEMICAL METHODS;    ZETA-VALENCE QUALITY;    HOLE DIPOLE-MOMENT;    DENSITY FUNCTIONALS;    BASIS-SETS;    INTERACTION ENERGIES;    HARTREE-FOCK;    ACCURATE;   

DOI  :  10.1103/PhysRevB.94.115144

来源: SCIE

【 摘 要 】

The strongly constrained and appropriately normed (SCAN) semilocal density functional [J. Sun, A. Ruzsinszky, and J. P. Perdew, Phys. Rev. Lett. 115, 036402 (2015)] obeys all 17 known exact constraints for meta-generalized-gradient approximations (meta-GGAs), and it includes some medium-range correlation effects. Long-range London dispersion interactions are still missing, but they can be accounted for via an appropriate correction scheme. In this study, we combine SCAN with an efficient London dispersion correction and show that lattice energies of simple organic crystals can be improved with the applied correction by 50%. The London-dispersion corrected SCAN meta-GGA outperforms all other tested London-dispersion corrected meta-GGAs for molecular geometries. Our method yields mean absolute deviations (MADs) for main group bond lengths that are consistently below 1 pm, rotational constants with MADs of 0.2%, and noncovalent distances with MADs below 1%. For a large database of general main group thermochemistry and kinetics (similar to 800 chemical species), one of the lowest weighted mean absolute deviations for long-range corrected meta-GGA functionals is achieved. Noncovalent interactions are of average quality, and hydrogen bonded systems in particular seem to suffer from overestimated polarization related to the self-interaction error of SCAN. We also discuss some consequences of numerical sensitivity encountered for meta-GGAs.

【 授权许可】

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