Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 12, Issue 8, Pages 3993-4003Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.6b00498
Keywords
-
Funding
- European Research Council (ERC)
- Region des Pays de la Loire [Marches -278845]
- LumoMat project
- French National Agency for Research [ANR-11-EQPX-0004]
Ask authors/readers for more resources
The accuracies of the excited-state dipole and quadrupole moments obtained by TD-DFT are assessed by considering 16 different exchange-correlation functionals and more than 30 medium and large molecules. Except for excited state presenting a significant charge-transfer character, a relatively limited dependency on the nature of the functional is found. It also turns out that while DFT ground-state dipole moments tend to be too large, the reverse trend is obtained for their excited-state counterparts, at least when hybrid functionals are used. Consequently, the TD-DFT excess dipole moments are often too small, an error that can be fortuitously corrected for charge-transfer transition by selecting a pure or a hybrid functional containing a small share of exact exchange. This error-cancelation phenomena explains the contradictory conclusions obtained in previous investigations. Overall, the largest correlation between CC2 and TD-DFT excess dipoles is obtained with M06-2X, but at the price of a nearly systematic underestimation of this property by ca. 1 D. For the excess quadrupole moments, the average errors are of the order of 0.2-0.6 D.angstrom for the set of small aromatic systems treated.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available