Free energy barriers for CO2 and N2 in zeolite NaKA: an ab initio molecular dynamics approach

Ab initio Molecular Dynamics (AIMD) is used with spatial constraints to estimate the free energy barriers of diffusion for CO2 and N2 gas molecules in zeolite NaA and KA. We investigate the extent to which the diffusion of these gas molecules is hindered, in the two separate cases of a smaller Na(+) ion or a larger K(+) ion blocking the 8-ring pore window. In contrast to classical Molecular Dynamics, AIMD performs these computations accurately and unbiased in the absence of empirical parameterization. Our work has resulted in stable and reliable force profiles. The profiles show that the larger K(+) ion effectively blocks the passage of both CO2 and N2 molecules while the smaller Na(+) ion will allow both molecules to pass. These results are a quantitative demonstration of the concept of pore blocking where we compute the effect, which the size of the respective cation occupying the pore window has on diffusive properties of each gas molecule. Hence, this effect can be altered through ion exchange to fine-tune the functionality of a specific zeolite as a molecular sieve.