☆ 4.7 Article

Double-Hybrid Density Functionals Provide a Balanced Description of Excited 1La and 1Lb States in Polycyclic Aromatic Hydrocarbons

JOURNAL OF CHEMICAL THEORY AND COMPUTATION (2011)

期刊

JOURNAL OF CHEMICAL THEORY AND COMPUTATION

卷 7, 期 10, 页码 3272-3277

出版社

AMER CHEMICAL SOC

DOI: 10.1021/ct200380v

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Chemistry, Physical Physics, Atomic, Molecular & Chemical

资金

Research School NRW-Molecules and Materials-A Common Design Principle
NRW Graduate School of Chemistry

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摘要

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.

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