A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions

Abstract

Abstract.We present a new local density functional, called M06-L, for main-group and transition element thermochemistry, thermochemical kinetics, and noncovalent interactions. The functional is designed to capture the main dependence of the exchangecorrelation energy on local spin density, spin density gradient, and spin kinetic energy density, and it is parametrized to satisfy the uniform-electron-gas limit and to have good performance for both main-group chemistry and transition metal chemistry. The M06-L functional and 14 other functionals have been comparatively assessed against 22 energetic databases. Among the tested functionals, which include the popular B3LYP, BLYP, and BP86 functionals as well as our previous M05 functional, the M06-L functional gives the best overall performance for a combination of main group thermochemistry, thermochemical kinetics, and organometallic, inorganometallic, biological, and noncovalent interactions. It is also does very well for predicting geometries and vibrational frequencies. Because of the computational advantages of local functionals, the present functional should be very useful for many applications in chemistry, especially for simulations on moderate-sized and large systems and when long time scales must be addressed.

Synergy of van der Waals and self-interaction corrections in transition metal monoxides

“…The vdW interaction can be roughly separated into an intermediate-range part and a long-range part. The former can be included in a semilocal functional within the exchange energy [46], being overestimated by LDA, barely included by the rev-B86b GGA [49] in revDF2, slightly included by PBE GGA, and about right in SCAN as well as the M06L [50] metaGGAs. Accordingly, we add a large vdWC to PBE, a small vdWC to SCAN, and none to revDF2 which already includes vdW via the vdW-DF2 correlation functional [51].…”

Self-consistent meta-generalized gradient approximation within the projector-augmented-wave method

“…Usually, MGGA functionals include either the Laplacian of the density [20][21][22] or the kinetic energy density 6,7,[23][24][25][26][27] . Some of them, however, include both ∇ 2 n σ and τ σ 17, 28,29 .…”

Testing the Jacob's ladder of density functionals for electronic structure and magnetism of rutileVO2

“…Some meta-GGA functionals have been well-developed and tested for various properties of atoms, molecules and solids [17,[19][20][21][22][23][24]. The testing of non-empirically derived meta-GGA functionals for magnetic structures of solid is still very rare.…”