title: Force-Field Development from Electronic Structure Calculations with Periodic Boundary Conditions: Applications to Gaseous Adsorption and Transport in Metal-Organic Frameworks.
abstract: We present a systematic and efficient methodology to derive accurate (nonpolarizable) force fields from periodic density functional theory (DFT) calculations for use in classical molecular simulations. The methodology requires reduced computation cost compared with other conventional ways. Moreover, the whole process is performed self-consistently in a fully periodic system. The force fields derived by using this methodology nicely predict the CO2 and H2O adsorption isotherms inside Mg-MOF-74, and is transferable to Zn-MOF-74; by replacing the Mg-CO2 interactions with the corresponding Zn-CO2 interactions, we obtain an accurate prediction of the corresponding isotherm. We have applied this methodology to address the effect of water on the separation of flue gases in these materials. In general, the mixture isotherms of CO2 and H2O calculated with these derived force fields show a significant reduction in CO2 uptake with the existence of trace amounts of water vapor. The effect of water, however, is found to be quantitatively different between Mg- and Zn-MOF-74.
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California, Berkeley , Berkeley, California, 94720, United States.
authors.forename: Li-Chiang
authors.initials: LC
authors.lastname: Lin
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California, Berkeley , Berkeley, California, 94720, United States.|Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California, 94720, United States.
authors.forename: Kyuho
authors.initials: K
authors.lastname: Lee
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota , Minneapolis, Minnesota, 55455, United States.
authors.forename: Laura
authors.initials: L
authors.lastname: Gagliardi
authors.affiliation: Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California, 94720, United States.|Department of Physics, University of California, Berkeley , Berkeley, California, 94720, United States.
authors.forename: Jeffrey B
authors.initials: JB
authors.lastname: Neaton
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of California, Berkeley , Berkeley, California, 94720, United States.|Department of Chemistry, University of California, Berkeley , Berkeley, California, 94720, United States.|Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, 94720, United States.
authors.forename: Berend
authors.initials: B
authors.lastname: Smit