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

C.A. Guido (1) , P. Cortona (1) , C. Adamo (2, 3)

1 SPMS - Laboratoire Structures, Propriétés et Modélisation des solides
2 LECIME - Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575)
3 IUF - Institut universitaire de France

We extend our previous definition of the metric !r for electronic excitations in the framework of the time-dependent density functional theory [C. A. Guido, P. Cortona, B. Mennucci, and C. damo, 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 ", permits applications in those situations where the !r-index is not helpful: transitions in centrosymmetric systems and Rydberg excitations. The "-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 " 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.

Domaines: Science des matériaux [cond-mat.mtrl-sci]

C.A. Guido, P. Cortona, C. Adamo. Effective electron displacements: A tool for time-dependent density functional theory computational spectroscopy. Journal of Chemical Physics, 2014, 140, pp.104101. ⟨10.1063/1.4867007⟩. ⟨hal-01053347⟩