Benchmarking the performance of time-dependent density functional methods

Abstract

The performance of 24 density functionals, including 14 meta-generalized gradient approximation (mGGA) functionals, is assessed for the calculation of vertical excitation energies against an experimental benchmark set comprising 14 small- to medium-sized compounds with 101 total excited states. The experimental benchmark set consists of singlet, triplet, valence, and Rydberg excited states. The global-hybrid (GH) version of the Perdew-Burke-Ernzerhoff GGA density functional (PBE0) is found to offer the best overall performance with a mean absolute error (MAE) of 0.28 eV. The GH-mGGA Minnesota 2006 density functional with 54 Hartree-Fock exchange (M06-2X) gives a lower MAE of 0.26 eV, but this functional encounters some convergence problems in the ground state. The local density approximation functional consisting of the Slater exchange and Volk-Wilk-Nusair correlation functional (SVWN) outperformed all non-GH GGAs tested. The best pure density functional performance is obtained with the local version of the Minnesota 2006 mGGA density functional (M06-L) with an MAE of 0.41 eV. © 2012 American Institute of Physics.