Static and dynamic descriptions of bond breaking/formation: a complementary view?
Ab initio molecular-dynamic simulations using density-functional theory and the recent atom-centered density-matrix propagation (ADMP) method were used to study the bond breaking and formation for a case-study substitution nucleophilic bimolecular reaction, namely, the Walden inversion. Using the atoms-in-molecule approach, we have performed a detailed analysis to investigate intra- and intermolecular charge transfer along the ADMP trajectory. These results were compared to those obtained considering a static approach, such as the intrinsic reaction path. In particular, the topological properties computed along the dynamic trajectory well evidence a stronger electron exchange tending to spontaneously maximize the rising covalent interaction. Furthermore, their analysis suggests that the bond formation mechanism involves a reactive intermediate with a bonding interaction stronger than in the final product.
Joubert
Laurent
L
Laboratoire d'Electrochimie et de Chimie Analytique, Centre National de la Recherche Scientifique (CNRS), Unité Mixte de Recherche (UMR) 7575, Ecole Nationale Supérieure de Chimie de Paris, Paris Cedex 05, France.
Adamo
Carlo
C