The adsorption and separation of greenhouse gases is an important issue in the field of environmental science and engineering.The self-assembly of supramolecular solid materials has important application in gas adsorption and storage.In this study,we develop force fields to describe gas adsorption in a novel porous pillarene-based supramolecular organic framework(SOF)by combining dispersion-corrected density functional theory calculations and classical atomistic simulations.The adsorption of CO2 in pillar[5]arene SOF(P5-SOF)was chosen to demonstrate the approach.On the basis of DFT-D calculations,a classical force field was then developed.The adsorption isotherms measured by first-principles-derived force field was found in excellent agreement with the experimental data.The solid-state porous P5-SOF shows high CO2 sorption capacities compared with known supramolecular macrocyclebased porous materials.In addition to the high CO2 capacity,P5-SOF also exhibits remarkable selectivities of CO2/N2,CO2/O2,CO2/CO.These properties indicate the suitable potential of porous P5-SOF in recycling and removing CO2 from flue gas.