Small Representative Databases for Testing and Validating Density Functionals and Other Electronic Structure Methods.

Abstract

Broad and diverse sets of accurate data provide useful metrics for assessing the performance of new theoretical methods. However, assessing methods against large databases can be an arduous task. Here, we present 17 representative energetic databases, defined as small databases whose errors and error spreads are representative of larger databases and which therefore can serve as efficient benchmarks for developing and testing electronic structure methods and density functionals. In 15 cases, the representative databases have 6 entries while being representative of larger databases with 14-107 entries, and in the other two cases, they have 14 entries while being representative of larger databases with 418-455 entries. The mean unsigned error (MUE) of 100 electronic structure methods on a given representative database is typically within about 8% of the MUE on its parent database, and the root-mean-square error (RMSE) is typically within about 11% of the RMSE on the parent database. Thus, the representative databases are quite successful in indicating accuracy while maintaining good diversity. The databases include both main-group and transition-metal compounds and reactions, and they include bond energies, reaction energies, barrier heights, noncovalent interactions, ionization potentials, and absolute energies.