Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections

TL;DR

This paper introduces two new long-range corrected hybrid density functionals, omegaM06-D3 and omegaB97X-D3, which incorporate improved dispersion corrections, achieving high accuracy across diverse chemical applications.

Contribution

The paper develops and validates two novel LC hybrid density functionals with enhanced dispersion corrections, outperforming previous functionals in various computational chemistry tasks.

Findings

omegaB97X-D3 outperforms omegaB97X-D in non-bonded interactions.

omegaM06-D3 shows superior performance in general applications.

Both functionals are accurate for thermochemistry, kinetics, and charge-transfer excitations.

Abstract

By incorporating the improved empirical atom-atom dispersion corrections from DFT-D3 [Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys. 2010, 132, 154104], two long-range corrected (LC) hybrid density functionals are proposed. Our resulting LC hybrid functionals, omegaM06-D3 and omegaB97X-D3, are shown to be accurate for a very wide range of applications, such as thermochemistry, kinetics, noncovalent interactions, frontier orbital energies, fundamental gaps, and long-range charge-transfer excitations, when compared with common global and LC hybrid functionals. Relative to omegaB97X-D [Chai, J.-D.; Head-Gordon, M. Phys. Chem. Chem. Phys. 2008, 10, 6615], omegaB97X-D3 (reoptimization of omegaB97X-D with improved dispersion corrections) is shown to be superior for non-bonded interactions, and similar in performance for bonded interactions, while omegaM06-D3 is shown to be superior for general applications.