title: The Fate of a Zwitterion in Water from ab Initio Molecular Dynamics: Monoethanolamine (MEA)-CO2.
abstract: Understanding 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.
authors.affiliation: Centre de Calcul Atomique et Moléculaire (CECAM), Ecole Polytechnique Fédérale de Lausanne, Switzerland.
authors.forename: Ciro A
authors.initials: CA
authors.lastname: Guido
authors.affiliation: Centre de Calcul Atomique et Moléculaire (CECAM), Ecole Polytechnique Fédérale de Lausanne, Switzerland.
authors.forename: Fabio
authors.initials: F
authors.lastname: Pietrucci
authors.affiliation: Centre de Calcul Atomique et Moléculaire (CECAM), Ecole Polytechnique Fédérale de Lausanne, Switzerland.
authors.forename: Grégoire A
authors.initials: GA
authors.lastname: Gallet
authors.affiliation: Centre de Calcul Atomique et Moléculaire (CECAM), Ecole Polytechnique Fédérale de Lausanne, Switzerland.|Institut de Théorie des Phénomènes Physiques, Ecole Polytechnique Fédérale de Lausanne, Switzerland.
authors.forename: Wanda
authors.initials: W
authors.lastname: Andreoni