Double-Hybrid Density Functionals Provide a Balanced Description of Excited L-1(a) and L-1(b) States in Polycyclic Aromatic Hydrocarbons

作者：Goerigk Lars; Grimme Stefan^*

来源：Journal of Chemical Theory and Computation, 2011, 7(10): 3272-3277.

DOI：10.1021/ct200380v

The time-dependent density functional theory (TD-DFT) double-hybrid methods TD-B2-PLYP and TD-B2GP-PLYP are applied to five linear and 12 nonlinear polycyclic aromatic hydrocarbons. The absolute errors compared to experiment for the two lowest-lying L-1(a) and L-1(b) excited states are evaluated and it is also tested whether the energetic order of those states and their energy difference is reproduced correctly. The results are compared to published CC2, global hybrid, and long-range corrected hybrid TD-DFT results. The two double-hybrids outmatch the other methods in terms of absolute and relative accuracy without an empirical adjustment of parameters. Although of different electronic character, both types of states are described on an equal footing by the double-hybrids. Particularly, the B2GP-PLYP functional yields very good results, which is in accordance with previous benchmarks.

• 出版日期2011-10