Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 9, Issue 1, Pages 28-32Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ct301071b
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Funding
- Swiss National Science Foundation [132081]
- Geneva Canton
- Vaud Canton
- foundation of Hans Wilsdorf
- foundation of Louis-Jeantet
- University of Geneva
- University of Lausanne
- Ecole Polytechnique Federale de Lausanne
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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.
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