C. Adamo et al., Accurate excitation energies from time-dependent density functional theory: Assessing the PBE0 model, J CHEM PHYS, 111(7), 1999, pp. 2889-2899
We analyze the performance of a density functional model obtained by combin
ing the Perdew-Burke-Erzenrhof (PBE) generalized gradient functional with a
predetermined amount of exact exchange for predicting vertical electronic
excitation energies within a time-dependent approach. Four molecules, namel
y, CO, H2CO, (CH3)(2)CO, and C2H4, have been chosen as benchmark cases. Our
results show that this model (PBE0) provides accurate excitations both to
valence and Rydberg states. Furthermore, the results are numerically close
to those obtained using asymptotically correct exchange-correlation functio
nals. The performance of the PBE0 model for predicting excitation energies
in larger molecules is assessed for benzene, pyridine, and naphthalene. Her
e, the PBE0 model provides results which are in fairly good agreement with
experimental data and of similar quality to those obtained by more sophisti
cated (and time-consuming) post-Hartree-Fock methods. (C) 1999 American Ins
titute of Physics. [S0021-9606(99)30531-6].