Extensive TD-DFT Benchmark: Singlet-Excited States of Organic Molecules

被引:960
作者
Jacquemin, Denis [1 ]
Wathelet, Valerie [1 ]
Perpete, Eric A. [1 ]
Adamo, Carlo [2 ]
机构
[1] Fac Univ Notre Dame Paix, Grp Chim Phys Theor & Struct, B-5000 Namur, Belgium
[2] Ecole Natl Super Chim Paris, Lab Electrochim & Chim Analyt, UMR CNRS ENSCP 7575, F-75321 Paris 05, France
关键词
DENSITY-FUNCTIONAL THEORY; POLARIZABLE CONTINUUM MODEL; EXCITATION-ENERGIES; UV/VIS SPECTRA; UV SPECTRA; CONFIGURATION-INTERACTION; ABSORPTION WAVELENGTH; ELECTRONIC EXCITATION; VISIBLE SPECTRA; KEY ROLE;
D O I
10.1021/ct900298e
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Extensive Time-Dependent Density Functional Theory (TD-DFT) calculations have been carried out in order to obtain a statistically meaningful analysis of the merits of a large number of functionals. To reach this goal, a very extended set of molecules (similar to 500 compounds, >700 excited states) covering a broad range of (bio)organic molecules and dyes have been investigated, Likewise, 29 functionals including LDA, GGA, meta-GGA, global hybrids, and long-range-corrected hybrids have been considered. Comparisons with both theoretical references and experimental measurements have been carried out. On average, the functionals providing the best match with reference data are, one the one hand, global hybrids containing between 22 and 25 of exact exchange (X3L P, B98, PBE0, and mPW1PW91) and on the other hand, a long-range-corrected hybrid with a less-rapidly increasing I-IF ratio, namely LC-omega PBE(20). Pure functionals tend to be less consistent, whereas functionals incorporating a larger fraction of exact exchange tend to underestimate significantly the transition energies. For most treated cases, the M05 and CAM-B3L. P schemes deliver fairly small deviations but (10 1101 Outperform standard hybrids such as X3L P or PBE0, at least within the vertical approximation. With the optimal functionals, one obtains mean absolute deviations smaller than 0.25 e, though the errors significantly depend on the Subset of molecules or states considered. As in illustration. PBE0 and LC-omega PBE(20) provide a mean absolute error of only 0.14 e for the 228 states related to neutral organic dyes but are completely off target for cyanine-like derivatives. On the basis of comparisons with theoretical estimates, it also turned Out that CC2 and TD-DFT errors are of the same order of magnitude, once the above-mentioned hybrids are selected.
引用
收藏
页码:2420 / 2435
页数:16
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