Guido, Ciro A.Pietrucci, FabioGallet, Gregoire A.Andreoni, Wanda2013-03-282013-03-282013-03-28201310.1021/ct301071bhttps://infoscience.epfl.ch/handle/20.500.14299/90959WOS:000313378700006Understanding the fundamental reactions accompanying the capture of carbon dioxide in amine solutions is critical for the design of high-performance solvents and requires an accurate modeling of the solute-solvent interaction. As a first step toward this goal, using ab initio molecular dynamics (Car-Parrinello) simulations, we investigate a zwitterionic carbamate, a species long proposed as intermediate in the formation of a stable carbamate, in a dilute aqueous solution. CO2 release and deprotonation are competitive routes for its dissociation and are both characterized by free-energy barriers of 6-8 kcal/mol. Water molecules play a crucial role in both pathways, resulting in large entropic effects. This is especially true in the case of CO2 release, which is accompanied by a strong reorganization of the solvent beyond the first coordination shell, leading to the formation of a water cage entrapping the solute (hydrophobic effect). Our results contrast with the assumptions of implicit solvent models.text::journal::journal article::research article