Developing semi-empirical water model for efficiently simulating temperature-dependent chemisorption of CO₂ in amine solvents

Abstract

Classical molecular dynamics (MD) simulations without bond forming/breaking cannot be used to model chemical reactions (CRs) among small molecules. Although the first-principle MD simulation can adequately describe CRs with explicit water molecules, such simulation is normally too costly for most researchers to afford. Generally, water molecules in a solvent can exert hydrophobic forces on reacting molecules, which yields a so-called caging effect that cannot be ignored when constructing a free energy landscape for reacting molecules. Many recently developed semi-empirical methods (such as DFTB, PM6 and xTB) are highly efficient for modeling CRs, however none of them can be directly used to model bulk water properly. Here, we developed a modified xTB approach that enables the simulation of CRs in explicit water. Using the chemisorption of CO2 by amines in water as an example application, we demonstrate that our approach yielded results comparable with the first-principle ones, while only using a limited computing resource. Potentially, our proposed semi-empirical water model can be utilized for the computational study of any CR in water.