Effect of Flexibility in Molecular Simulations of Carbon Dioxide Adsorption and Diffusion in a Cuprous Triazolate Framework

Baucom, Tiernan; Budhathoki, Samir; Steckel, Janice A.

doi:10.1021/acs.jpcc.3c03012

Effect of Flexibility in Molecular Simulations of Carbon Dioxide Adsorption and Diffusion in a Cuprous Triazolate Framework

Journal Article · Tue Aug 29 00:00:00 EDT 2023 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.3c03012· OSTI ID:1999216

^[1]; Budhathoki, Samir ^[2]; ^[2]

National Energy Technology Laboratory (NETL), Pittsburgh, PA (United States); Oak Ridge Institute for Science and Education (ORISE), Oak Ridge, TN (United States); University of Michigan, Ann Arbor, MI (United States)
National Energy Technology Laboratory (NETL), Pittsburgh, PA (United States)

Using fixed atom force fields to model gas adsorption in flexible metal organic frameworks (MOFs) is known to pose difficulties in accurately reproducing and predicting experimental results. This paper studies the difference in accuracy between flexible and fixed atom force fields in reproducing CO₂ adsorption measurements in MAF-2 ([Cu(etz)]∞ (MAF-2, Hetz) 3,5-diethyl-1,2,4-triazole), an NbO-type triazolate scaffold with a bcu cavity system and attached ethyl groups. The flexible force field used to run the hybrid molecular dynamics and grand canonical Monte Carlo calculations were generated using the QuickFF software incorporating van der Waals parameters from the Universal Force Field (UFF) and density derived electrostatic and chemical (DDEC) charges. The fixed atom force field used was composed of UFF van der Waals parameters together with DDEC charges. The calculations were run at 298 K and at pressures of 0.1, 0.3, 0.5, 0.8, and 1 bar. It was observed that for this MOF the rigid force field overpredicted gas adsorption, whereas the flexible force field values closely matched experimental data. In the flexible structure, the freely moving ethyl groups of MAF-2 hindered adsorption, reducing the interaction energy between CO₂ and the N atoms of the triazolate framework as well as reducing the size of the largest cavity diameter. Here, the combination of these factors led to improved prediction of adsorption values with the flexible forcefield as compared to the rigid forcefield, demonstrating the need for modeling MOFs in a way more indicative of their behavior.

View Accepted Manuscript (DOE)

Research Organization:: National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy (FE)

OSTI ID:: 1999216

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 35 Vol. 127; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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