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Guido CA, Cortona P, Mennucci B, et al. On the Metric of Charge Transfer Molecular Excitations: A Simple Chemical Descriptor. J Chem Theory Comput. 2013;9(7):3118-26doi: 10.1021/ct400337e.
Guido, C. A., Cortona, P., Mennucci, B., & Adamo, C. (2013). On the Metric of Charge Transfer Molecular Excitations: A Simple Chemical Descriptor. Journal of chemical theory and computation, 9(7), 3118-26. https://doi.org/10.1021/ct400337e
Guido, Ciro A, et al. "On the Metric of Charge Transfer Molecular Excitations: A Simple Chemical Descriptor." Journal of chemical theory and computation vol. 9,7 (2013): 3118-26. doi: https://doi.org/10.1021/ct400337e
Guido CA, Cortona P, Mennucci B, Adamo C. On the Metric of Charge Transfer Molecular Excitations: A Simple Chemical Descriptor. J Chem Theory Comput. 2013 Jul 09;9(7):3118-26. doi: 10.1021/ct400337e. Epub 2013 Jun 18. PMID: 26583991.
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J Chem Theory Comput. 2013 Jul 09;9(7):3118-26. doi: 10.1021/ct400337e. Epub 2013 Jun 18.

On the Metric of Charge Transfer Molecular Excitations: A Simple Chemical Descriptor.

Journal of chemical theory and computation

Ciro A Guido, Pietro Cortona, Benedetta Mennucci, Carlo Adamo

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 Chemistry, University of Pisa , Via Risorgimento 35, 56126 Pisa, Italy.
  3. Laboratoire d'Électrochimie, Chimie des Interfaces et Modélisation pour l'Energie, CNRS UMR-7575, Chimie ParisTech , 11 rue P. et M. Curie, F-75231 Paris Cedex 05, France.
  4. Institut Universitaire de France , 103 Bd Saint-Michel, F-75005 Paris, France.

PMID: 26583991 DOI: 10.1021/ct400337e

Abstract

A new index is defined with the aim of further exploring the metric of excited electronic states in the framework of the time-dependent density functional theory. This descriptor, called Δr, is based on the charge centroids of the orbitals involved in the excitations and can be interpreted in term of the hole-electron distance. The tests carried out on a set of molecules characterized by a significant number of charge-transfer excitations well illustrate its ability in discriminating between short (Δr ≤ 1.5 Å) and long-range (Δr ≥ 2.0 Å) excitations. On the basis of the well-known pitfalls of TD-DFT, its values can be then associated to the functional performances in reproducing different type of transitions and allow for the definition of a "trust radius" for GGA and hybrid functionals. The study of other systems, including some well-known difficult cases for other metric descriptors, gives further evidence of the high discrimination power of the proposed index. The combined use with other density or orbital-based descriptors is finally suggested to have a reliable diagnostic test of TD-DFT transitions.

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