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Guido CA, Jacquemin D, Adamo C, et al. Electronic Excitations in Solution: The Interplay between State Specific Approaches and a Time-Dependent Density Functional Theory Description. J Chem Theory Comput. 2015;11(12):5782-90doi: 10.1021/acs.jctc.5b00679.
Guido, C. A., Jacquemin, D., Adamo, C., & Mennucci, B. (2015). Electronic Excitations in Solution: The Interplay between State Specific Approaches and a Time-Dependent Density Functional Theory Description. Journal of chemical theory and computation, 11(12), 5782-90. https://doi.org/10.1021/acs.jctc.5b00679
Guido, Ciro A, et al. "Electronic Excitations in Solution: The Interplay between State Specific Approaches and a Time-Dependent Density Functional Theory Description." Journal of chemical theory and computation vol. 11,12 (2015): 5782-90. doi: https://doi.org/10.1021/acs.jctc.5b00679
Guido CA, Jacquemin D, Adamo C, Mennucci B. Electronic Excitations in Solution: The Interplay between State Specific Approaches and a Time-Dependent Density Functional Theory Description. J Chem Theory Comput. 2015 Dec 08;11(12):5782-90. doi: 10.1021/acs.jctc.5b00679. Epub 2015 Nov 06. PMID: 26642990.
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J Chem Theory Comput. 2015 Dec 08;11(12):5782-90. doi: 10.1021/acs.jctc.5b00679. Epub 2015 Nov 06.

Electronic Excitations in Solution: The Interplay between State Specific Approaches and a Time-Dependent Density Functional Theory Description.

Journal of chemical theory and computation

Ciro A Guido, Denis Jacquemin, Carlo Adamo, Benedetta Mennucci

Affiliations

  1. Dipartimento di Chimica e Chimica Industriale, Università di Pisa , Via Moruzzi 13, 56124 Pisa, Italy.
  2. Laboratoire CEISAM - UMR CNRS 6230, Université de Nantes , 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.
  3. Institut Universitaire de France , 103, bd. Saint-Michel, F-75005 Paris Cedex 05, France.
  4. Institut de Recherche Chimie Paris, PSL University Chimie ParisTech CNRS , 11 rue P. et M. Curie, F-75005 Paris, France.

PMID: 26642990 DOI: 10.1021/acs.jctc.5b00679

Abstract

We critically analyze the performances of continuum solvation models when coupled to time-dependent density functional theory (TD-DFT) to predict solvent effects on both absorption and emission energies of chromophores in solution. Different polarization schemes of the polarizable continuum model (PCM), such as linear response (LR) and three different state specific (SS) approaches, are considered and compared. We show the necessity of introducing a SS model in cases where large electron density rearrangements are involved in the excitations, such as charge-transfer transitions in both twisted and quadrupolar compounds, and underline the very delicate interplay between the selected polarization method and the chosen exchange-correlation functional. This interplay originates in the different descriptions of the transition and ground/excited state multipolar moments by the different functionals. As a result, the choice of both the DFT functional and the solvent polarization scheme has to be consistent with the nature of the studied electronic excitation.

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