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Title: Effective electron displacements: A tool for time-dependent density functional theory computational spectroscopy

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.
Authors:
;  [1] ;  [2] ;  [3]
  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. 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)
  3. (France)
Publication Date:
OSTI Identifier:
22253469
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 10; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DENSITY FUNCTIONAL METHOD; ELECTRON DENSITY; EXCITATION; SPECTROSCOPY; TIME DEPENDENCE