Aurélien de la Lande

Considering as test case a family of organic rod like push–pull molecules, we derived and applied density based index enabling the description and diagnostic of the electronic density evolution in real time‐time dependent density functional theory (RT‐TDDFT) simulations. In particular, both the charge transfer (CT) distance and a diagnostic index, the D CT and M AC RT respectively, were computed on the fly from the density distribution obtained at a given time and the reference ground state density and their mean values were compared with what obtained at Linear Response‐TDDFT level. Besides giving a way of analyzing the density redistribution occurring in time, these tools allowed to show how RT‐TDDFT, which is definitely a powerful method to model the evolution of the density in CT or charge separation processes, can be affected by the same artifacts known for LR‐TDDFT approaches and, particularly, to those related to the use of approximate exchange correlation functionals. The analysis here performed allowed to identify and discard on fly the electronic configurations corresponding to spurious situations.