Reaching quantum accuracy in predicting adsorption properties for ethane/ethene in ZIF-8 at the low pressure regime

S. Ravichandran, M. Najafi, R. Goeminne, J. F. M. Denayer, V. Van Speybroeck, L. Vanduyfhuys
Journal of Chemical Theory and Computation
2024
A1

Abstract 

Nanoporous materials in the form of metal−organicframeworks such as zeolitic imidazolate framework-8 (ZIF-8) arepromising membrane materials for the separation of hydrocarbonmixtures. To compute the adsorption isotherms in suchadsorbents, grand canonical Monte Carlo simulations have provento be very useful. The quality of these isotherms depends on theaccuracy of adsorbate−adsorbent interactions, which are mostlydescribed using force fields owing to their low computational cost.However, force field predictions of adsorption uptake often showdiscrepancies from experiments at low pressures, providing theneed for methods that are more accurate. Hence, in this work, wepropose and validate two novel methodologies for the ZIF-8/ethane and ethene systems; a benchmarking methodology toevaluate the performance of any given force field in describing adsorption in the low-pressure regime and a refinement procedure torescale the parameters of a force field to better describe the host−guest interactions and provide for simulation isotherms with closeagreement to experimental isotherms. Both methodologies were developed based on a reference Henry coefficient, computed withthe PBE-MBD functional using the importance sampling technique. The force field rankings predicted by the benchmarkingmethodology involve the comparison of force field derived Henry coefficients with the reference Henry coefficients and ranking theforce fields based on the disparities between these Henry coefficients. The ranking from this methodology matches the rankingsmade based on uptake disparities by comparing force field derived simulation isotherms to experimental isotherms in the low-pressure regime. The force field rescaling methodology was proven to refine even the worst performing force field in UFF/TraPPE.The uptake disparities of UFF/TraPPE improved from 197% and 194% to 11% and 21% for ethane and ethene, respectively. Theproposed methodology is applicable to predict adsorption across nanoporous materials and allows for rescaled force fields to reachquantum accuracy without the need for experimental input.