On the accuracy of intermolecular interactions and charge transfer: the case of TTF-CA

Pilar García (1) , Slimane Dahaoui (1) , Claudine Katan (2) , Mohamed Souhassou (1) , Claude Lecomte (1)

1 CRM2 - Cristallographie, Résonance Magnétique et Modélisations
2 SESO - Synthèse et électrosynthèse organiques

High-resolution X-ray diffraction experiments and state of the art density functional theory calculations have been performed. The validity of the atoms in molecules approach is tested for the neutral-ionic transition of TTF-CA which involves a transfer of less than one electron between the donor and acceptor molecules. Foremost, crystallographical data have been reassessed along the temperature-induced neutral-ionic phase transition undergone by this charge transfer complex. Based on accurate X-ray structures at 105 and 15 K, topological analysis of both DFT and the experimental multipolar electron densities allowed detailed characterization of intra-and interstack intermolecular interactions. Direct quantification of the intermolecular charge transfer and the dipole moment are discussed.

Domaines: Chimie théorique et/ou physique

Pilar García, Slimane Dahaoui, Claudine Katan, Mohamed Souhassou, Claude Lecomte. On the accuracy of intermolecular interactions and charge transfer: the case of TTF-CA. Faraday Discussions, 2007, 135, pp.217-235. ⟨10.1039/B606642A⟩. ⟨hal-01416922⟩