Employing Range Separation on the meta-GGA Rung: New Functional Suitable for Both Covalent and Noncovalent Interactions

Abstract

We devise a scheme for converting an existing exchange functional into its range-separated hybrid variant. The underlying exchange hole of the Becke-Roussel type has the exact second-order expansion in the interelectron distance. The short-range part of the resulting range-separated exchange energy depends on the kinetic energy density and the Laplacian even if the base functional lacks the dependence on these variables. The most successful practical realization of the scheme, named LC-PBETPSS, combines the range-separated PBE exchange lifted to the hybrid meta-GGA rung and the TPSS correlation. The value of the range-separation parameter is estimated theoretically and confirmed by empirical optimization. The D3 dispersion correction is recommended for all energy computations employing the presented functional. Numerical tests show remarkably robust performance of the method for noncovalent interaction energies, barrier heights, main-group thermochemistry, and excitation energies.

References in corpus (9)

• Climbing the Density Functional Ladder: Non-Empirical Meta-Generalized Gradient Approximation Designed for Molecules and Solids
• Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections
• A well-tempered density functional theory of electrons in molecules
• Quasiparticle spectra from a non-empirical optimally-tuned range-separated hybrid density functional
• Charge-transfer excitations in molecular donor-acceptor complexes within the many-body Bethe-Salpeter approach
• Long-range corrected hybrid meta-generalized-gradient approximations with dispersion corrections
• Assessment of density functional methods with correct asymptotic behavior
• Range-separated meta-GGA functional designed for noncovalent interactions
• A first-principles-based correlation functional for harmonious connection of short-range correlation and long-range dispersion

Cited by in corpus (3)

• Semilocal exchange hole with an application to range-separation density functional
• The nature of three-body interactions in DFT: exchange and polarization effects
• Simple exchange hole models for long-range-corrected density functionals