Benchmarking the performance of time-dependent density functional methods
| Title | Benchmarking the performance of time-dependent density functional methods |
| Publication Type | Journal Article |
| Year of Publication | 2012 |
| Authors | Leang SS, Zahariev F, Gordon MS |
| Journal Title | Journal of Chemical Physics |
| Volume | 136 |
| Pages | 104101 |
| Date Published | 03 |
| Type of Article | Article |
| ISBN Number | 0021-9606 |
| Accession Number | WOS:000301664600002 |
| Keywords | configuration-interaction, electron-impact, energy-loss spectroscopy, excited-state calculations, generalized gradient approximation, kohn-sham orbitals, main-group thermochemistry, molecular-orbital methods, multiphoton ionization, MULTIREFERENCE, RESONANT, spectroscopy, vertical excitation-energies |
| 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. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3689445] |
| URL | <Go to ISI>://WOS:000301664600002 |
| DOI | 10.1063/1.3689445 |
| Alternate Journal | J. Chem. Phys. |
