We extend our previous definition of the metric Δr for electronic excitations in the framework of the time-dependent density functional theory [C. A. Guido, P. Cortona, B. Mennucci, and C. Adamo, J. Chem. Theory Comput. 9, 3118 (2013)], by including a measure of the difference of electronic position variances in passing from occupied to virtual orbitals. This new definition, called Γ, permits applications in those situations where the Δr-index is not helpful: transitions in centrosymmetric systems and Rydberg excitations. The Γ-metric is then extended by using the Natural Transition Orbitals, thus providing an intuitive picture of how locally the electron density changes during the electronic transitions. Furthermore, the Γ values give insight about the functional performances in reproducing different type of transitions, and allow one to define a “confidence radius” for GGA and hybrid functionals.
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14 March 2014
Research Article|
March 10 2014
Effective electron displacements: A tool for time-dependent density functional theory computational spectroscopy
Ciro A. Guido;
Ciro A. Guido
a)
1Laboratoire Structures,
Propriétés et Modélisation des Solides (SPMS)
, CNRS UMR 8580, École Centrale Paris, Grande Voie des Vignes, F-92295 Châtenay-Malabry, France
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Pietro Cortona;
Pietro Cortona
1Laboratoire Structures,
Propriétés et Modélisation des Solides (SPMS)
, CNRS UMR 8580, École Centrale Paris, Grande Voie des Vignes, F-92295 Châtenay-Malabry, France
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Carlo Adamo
Carlo Adamo
2Laboratoire 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
3Institut Universitaire de France,
103 Bd Saint-Michel
, F-75005 Paris, France
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a)
Electronic mail: [email protected]
J. Chem. Phys. 140, 104101 (2014)
Article history
Received:
November 27 2013
Accepted:
February 14 2014
Citation
Ciro A. Guido, Pietro Cortona, Carlo Adamo; Effective electron displacements: A tool for time-dependent density functional theory computational spectroscopy. J. Chem. Phys. 14 March 2014; 140 (10): 104101. https://doi.org/10.1063/1.4867007
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