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Guido CA, Knecht S, Kongsted J, et al. Benchmarking Time-Dependent Density Functional Theory for Excited State Geometries of Organic Molecules in Gas-Phase and in Solution. J Chem Theory Comput. 2013;9(5):2209-20doi: 10.1021/ct400021c.
Guido, C. A., Knecht, S., Kongsted, J., & Mennucci, B. (2013). Benchmarking Time-Dependent Density Functional Theory for Excited State Geometries of Organic Molecules in Gas-Phase and in Solution. Journal of chemical theory and computation, 9(5), 2209-20. https://doi.org/10.1021/ct400021c
Guido, Ciro A, et al. "Benchmarking Time-Dependent Density Functional Theory for Excited State Geometries of Organic Molecules in Gas-Phase and in Solution." Journal of chemical theory and computation vol. 9,5 (2013): 2209-20. doi: https://doi.org/10.1021/ct400021c
Guido CA, Knecht S, Kongsted J, Mennucci B. Benchmarking Time-Dependent Density Functional Theory for Excited State Geometries of Organic Molecules in Gas-Phase and in Solution. J Chem Theory Comput. 2013 May 14;9(5):2209-20. doi: 10.1021/ct400021c. Epub 2013 Apr 05. PMID: 26583715.
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J Chem Theory Comput. 2013 May 14;9(5):2209-20. doi: 10.1021/ct400021c. Epub 2013 Apr 05.

Benchmarking Time-Dependent Density Functional Theory for Excited State Geometries of Organic Molecules in Gas-Phase and in Solution.

Journal of chemical theory and computation

Ciro A Guido, Stefan Knecht, Jacob Kongsted, Benedetta Mennucci

Affiliations

  1. Laboratoire Structures, Propriétés et Modélisation des Solides (SPMS), CNRS UMR 8580, École Centrale Paris , Grande Voie des Vignes, F-92295 Châtenay-Malabry, France.
  2. Department of Physics, Chemistry and Pharmacy, University of Southern Denmark , Campusvej 55, 5230 Odense M, Denmark.
  3. Dipartimento di Chimica e Chimica Industriale, Università di Pisa , via Risorgimento 35, I-56126 Pisa, Italy.

PMID: 26583715 DOI: 10.1021/ct400021c

Abstract

We analyze potentials and limits of the Time-Dependent Density Functional Theory (TD-DFT) approach for the determination of excited-state geometries of organic molecules in gas-phase and in solution. Three very popular DFT exchange-correlation functionals, two hybrids (B3LYP and PBE0) and one long-range corrected (CAM-B3LYP), are here investigated, and the results are compared to the correlated RI-CC2 wave function approach. Solvent effects are further analyzed by means of a polarizable continuum model. A total of 15 organic chromophores (including both small molecules and larger push-pull systems) are considered as prototypes of n → π* and π → π* singlet excitations. Our analysis allows to point out specific correlations between the accuracy of the various functionals and the type of excitation and/or the type of chemical bonds involved. We find that while the best ground-state geometries are obtained with PBE0 and B3LYP, CAM-B3LYP yields the most accurate description of electronic and geometrical characteristics of excited states, both in gas-phase and in solution.

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