A General Database for Main Group Thermochemistry, Kinetics, and Noncovalent Interactions − Assessment of Common and Reparameterized (meta-)GGA Density Functionals

Abstract

We present a quantum chemistry benchmark database for general main group thermochemistry, kinetics, and noncovalent interactions (GMTKN24). It is an unprecedented compilation of 24 different, chemically relevant subsets that either are taken from already existing databases or are presented here for the first time. The complete set involves a total of 1.049 atomic and molecular single point calculations and comprises 731 data points (relative chemical energies) based on accurate theoretical or experimental reference values. The usefulness of the GMTKN24 database is shown by applying common density functionals on the (meta-)generalized gradient approximation (GGA), hybrid-GGA, and double-hybrid-GGA levels to it, including an empirical London dispersion correction. Furthermore, we refitted the functional parameters of four (meta-)GGA functionals based on a fit set containing 143 systems, comprising seven chemically different problems. Validation against the GMTKN24 and the molecular structure (bond lengths) databases shows that the reparameterization does not change bond lengths much, whereas the description of energetic properties is more prone to the parameters' values. The empirical dispersion correction also often improves for conventional thermodynamic problems and makes a functional's performance more uniform over the entire database. The refitted functionals typically have a lower mean absolute deviation for the majority of subsets in the proposed GMTKN24 set. This, however, is also often accompanied at the expense of poor performance for a few other important subsets. Thus, creating a broadly applicable (and overall better) functional by just reparameterizing existing ones seems to be difficult. Nevertheless, this benchmark study reveals that a reoptimized (i.e., empirical) version of the TPSS-D functional (oTPSS-D) performs well for a variety of problems and may meet the standards of an improved functional. We propose validation against this new compilation of benchmark sets as a definitive way to evaluate a new quantum chemical method's true performance.