Carbon Capture and Storage (CCS) is one of the main options for carbon dioxide mitigation. Capture processes based on CO2 dissolution in alcanolamine solutions are considered among the most adequate methods for decarbonation of post-combustion effluents1. However, the energetic costs of avoided CO2 must be significantly reduced before process integration into industrial sites. The understanding of molecular interactions involved in {CO2+water+alcanolamine} systems is essential for optimizing gas dissolution and reducing process cost. The aim of this presentation is to compare thermodynamic properties of {alcanolmine+water} mixtures obtained experimentally and from molecular simulations. Molecular simulation provides a detailed microscopic view into thermodynamics and transport properties and is complementary to experimental measurements. Simulation is also a promising tool for the prediction of properties required to design capture process. The insights into microscopic structure and energetics of {alcanolamine+water} mixtures obtained from simulation, such as differences in hydrogen-bond interactions between different alcanolamines, contribute to improve structure-property relationships. A force field adapted to describe alkanolamines containing the N-C-C-O backbone2 was developed, taking into account the polar environment. This new force field was validated through to prediction of enthalpic and volumetric properties of seven alcanolamines, which are methyl- and ethyl-substituted monoethanolamine (MEA). The force field was then used to calculate the enthalpy of mixing alcanolamines with water. Results are compared to experimental data obtained using mixing calorimetry using both flow mixing and titration calorimeters. (1) Arcis, H.; Ballerat-Busserolles, K.; Rodier, L.; Coxam, J.-Y. J. Chem. Eng. Data 2011, 56, 3351-3362. (2) Simond M.R.; Ballerat-Busserolles K.; Coxam J-Y.; Pádua A.A.H. J. Phys. Chem. B 2012, submitted.