Theoretical insights on electron donor–acceptor interactions involving carbon dioxide

• Published in: Chemical physics letters 2014-05, Vol.601, p.98-102
• Main Authors: San-Fabián, Emilio, Ingrosso, Francesca, Lambert, Alexandrine, Bernal-Uruchurtu, Margarita I., Ruiz-López, Manuel F.
• Format: Article
• Language: English
• Subjects: Chemical Sciences; or physical chemistry; Theoretical and
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2014.03.084

[Display omitted] •We study the potential energy surface of the acetone–carbon dioxide complex with ab initio methods.•We analyze the contributions to the interaction energy with variational and perturbative approaches.•We describe non-conventional structures in which dispersion energy plays a key role.•We show that current density functional theory methods are unsuitable to describe this type of complexes. Electron donor–acceptor (EDA) interactions are widely involved in chemistry and their understanding is essential to design new technological applications in a variety of fields ranging from material sciences and chemical engineering to medicine. In this Letter, we study EDA complexes of carbon dioxide with ketones using several ab initio and density functional theory methods. Energy contributions to the interaction energy have been analyzed in detail using both variational and perturbational treatments. Dispersion energy has been shown to play a key role in explaining the high stability of a non-conventional structure, which can roughly be described by a cooperative EDA interaction.