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J Chem Theory Comput. 2014 Apr 8;10(4):1677-85. doi: 10.1021/ct5000617. Epub 2014 Mar 11.

Performance of an Optimally Tuned Range-Separated Hybrid Functional for 0-0 Electronic Excitation Energies.

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Laboratoire CEISAM-UMR CNRS 6230, Université de Nantes , 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.
Institut Universitaire de France , 103, bd Saint-Michel, F-75005 Paris Cedex 05, France.
Department of Chemistry, University at Buffalo, State University of New York , Buffalo, New York 14260-3000, United States.
Laboratoire LECIME-UMR CNRS 7575, Chimie-ParisTech , 11 rue P. et M. Curie, F-75231 Paris Cedex 05, France.


Using a set of 40 conjugated molecules, we assess the performance of an "optimally tuned" range-separated hybrid functional in reproducing the experimental 0-0 energies. The selected protocol accounts for the impact of solvation using a corrected linear-response continuum approach and vibrational corrections through calculations of the zero-point energies of both ground and excited-states and provides basis set converged data thanks to the systematic use of diffuse-containing atomic basis sets at all computational steps. It turns out that an optimally tuned long-range corrected hybrid form of the Perdew-Burke-Ernzerhof functional, LC-PBE*, delivers both the smallest mean absolute error (0.20 eV) and standard deviation (0.15 eV) of all tested approaches, while the obtained correlation (0.93) is large but remains slightly smaller than its M06-2X counterpart (0.95). In addition, the efficiency of two other recently developed exchange-correlation functionals, namely SOGGA11-X and ωB97X-D, has been determined in order to allow more complete comparisons with previously published data.


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