How Accurate Is Density Functional Theory at Predicting Dipole Moments? An Assessment Using a New Database of 200 Benchmark Values

Abstract

Dipole moments are a simple, global measure of the accuracy of the electron density of a polar molecule. Dipole moments also affect the interactions of a molecule with other molecules as well as electric fields. To directly assess the accuracy of modern density functionals for calculating dipole moments, we have developed a database of 200 benchmark dipole moments, using coupled cluster theory through triple excitations, extrapolated to the complete basis set limit. This new database is used to assess the performance of 88 popular or recently developed density functionals. The results suggest that double hybrid functionals perform the best, yielding dipole moments within about 3.6-4.5% regularized RMS error versus the reference values-which is not very different from the 4% regularized RMS error produced by coupled cluster singles and doubles. Many hybrid functionals also perform quite well, generating regularized RMS errors in the 5-6% range. Some functionals, however, exhibit large outliers, and local functionals in general perform less well than hybrids or double hybrids.