Charge distribution in metal organic framework materials: transferability to a preliminary molecular simulation study...

Density functional theory calculations have been performed in order to extract the charge distribution in the aluminium-containing MIL-53 structure, to allow further computational studies of adsorption in these materials. Both cluster and periodic methods have been used and the charges calculated for each atom constituting the organic and inorganic part of the material, were discussed. Preliminary grand canonical Monte Carlo simulations, based on a consistent set of potential parameters and this newly derived charge distribution, predicted for enthalpies of adsorption for CO(2) at low coverage in the "large" and "narrow" pore versions of MIL-53 (Al) to be significantly different. These calculated enthalpies reproduced the two distinct ranges of values observed by microcalorimetry on either side of 6 bars quite well. This agreement between experiment and simulation validated our previous assumption, suggesting a structural switching of the hybrid material during the adsorption process. The microscopic mode of interaction between the hybrid porous framework and the CO(2) adsorption was then carefully analysed in both of the MIL-53 (Al) structures.