DFT-Derived Force Fields for Modeling Hydrocarbon Adsorption in MIL-47(V)

Kulkarni, Ambarish; Sholl, David S.

doi:10.1021/acs.langmuir.5b01193

Cited by 35 publications

(56 citation statements)

References 96 publications

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“…It has been shown that generic force fields might not sample all relevant portions of the potential energy surface (PES). 65 We therefore extracted 100 configurations from snapshots of GCMC simulations (at 298 K and 1 bar) using all five force fields considered in this work, leading to a total set of 500 configurations. For the united-atom models, only the position of the carbon atom of methane can be extracted from the GCMC simulations: the orientation of the hydrogen atoms is in these cases determined randomly.…”

Section: Resultsmentioning

confidence: 99%

Methane Adsorption in Zr-Based MOFs: Comparison and Critical Evaluation of Force Fields

et al. 2017

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The search for nanoporous materials that are highly performing for gas storage and separation is one of the contemporary challenges in material design. The computational tools to aid these experimental efforts are widely available, and adsorption isotherms are routinely computed for huge sets of (hypothetical) frameworks. Clearly the computational results depend on the interactions between the adsorbed species and the adsorbent, which are commonly described using force fields. In this paper, an extensive comparison and in-depth investigation of several force fields from literature is reported for the case of methane adsorption in the Zr-based Metal–Organic Frameworks UiO-66, UiO-67, DUT-52, NU-1000, and MOF-808. Significant quantitative differences in the computed uptake are observed when comparing different force fields, but most qualitative features are common which suggests some predictive power of the simulations when it comes to these properties. More insight into the host–guest interactions is obtained by benchmarking the force fields with an extensive number of ab initio computed single molecule interaction energies. This analysis at the molecular level reveals that especially ab initio derived force fields perform well in reproducing the ab initio interaction energies. Finally, the high sensitivity of uptake predictions on the underlying potential energy surface is explored.

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Section: Resultsmentioning

confidence: 99%

Methane Adsorption in Zr-Based MOFs: Comparison and Critical Evaluation of Force Fields

et al. 2017

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“…Several sets of LJ parameters for CH4 have been derived which are capable of predicting the behaviour of the bulk fluid in simulation, of which the TraPPE force field [37] is most commonly applied in studies of adsorption. Although a number of groups have derived framework LJ parameters for specific MOF-guest systems [38,39,40], the majority of studies make use of one of several generic force fields, of which the most common are UFF, DREIDING and OPLS-AA. Both UFF and DREIDING were developed and tested for their ability to predict crystal structures, bond lengths and bond angles for organic [25,41] and, in the case of UFF, organometallic molecular complexes [42], while OPLS-AA was developed to correctly reproduce properties of bulk organic liquids, such as the heat of vaporisation and liquid density [26,27].…”

Section: Force Field-based Calculationsmentioning

confidence: 99%

The right isotherms for the right reasons? Validation of generic force fields for prediction of methane adsorption in metal-organic frameworks

Lennox

Bound

Henley

et al. 2017

Molecular Simulation

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In recent years, the use of computational tools to aid in the evaluation, understanding and design of advanced porous materials for gas storage and separation processes has become ever-more widespread. High-performance computing facilities have become more powerful and more accessible and molecular simulation of gas adsorption has become routine, often involving the use of a number of default and commonly-used parameters as a result. In this work, we consider the application of molecular simulation in one particular field of adsorption -the prediction of methane adsorption in metal-organic frameworks in the low-loading regime -and employ a range of computational techniques to evaluate the appropriateness of many commonly chosen simulation parameters to these systems. In addition to confirming the power of relatively simple generic force fields to quickly and accurately predict methane adsorption isotherms in a range of MOFs, we demonstrate that these force fields are capable of providing detailed molecular-level information which is in very good agreement with quantum chemical predictions. We highlight a number of chemical systems in which molecular-level insight from generic force fields should be approached with a degree of caution and provide some general recommendations for best-practice in simulations of CH4 adsorption in MOFs.

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“…A pragmatic approach is the derivation of improved parameter sets from density-functional theory (DFT) calculations of adsorption energies at the CUS [41][42][43][44][47][48][49]. This strategy has yielded good results for alkanes, alkenes and alkynes in CUS-containing MOFs [19,43,44,[50][51][52][53][54].…”

Section: Introductionmentioning

confidence: 99%

A computational study of the interaction of C2 hydrocarbons with CuBTC

Afonso

Toda

Gomes

et al. 2020

Computational Materials Science

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The adsorptions of ethane, ethene, and ethyne over the coordinatively unsaturated sites (CUS) of copper (II) benzene-1,3,5-tricarboxylate (CuBTC) were studied by means of density functional theory (DFT), using both cluster or periodic models. Exchange-correlation functionals from different rungs of the Jacobs ladder of the DFT were used and energies were corrected for the basis superposition error either through extrapolation to the complete basis set limit or upon the consideration of the Counterpoise method. From the calculated data, it was found that the adsorbate to CUS distances decrease in the order ethane > ethene ≈ ethyne and that the strength of adsorption increase in the order ethane to ethyne to ethene. The energies of interactions of ethene and ethyne with the CUS of CuBTC are approximately the double of that calculated for ethane. The calculated adsorption energies and geometries are in very satisfactory agreement with the available experimental results. The results of topological analyses confirm that the unsaturated bonds of ethene and ethyne form open shell like bonds with the CUS while interaction with ethane have predominant closed shell character.

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DFT-Derived Force Fields for Modeling Hydrocarbon Adsorption in MIL-47(V)

Cited by 35 publications

References 96 publications

Methane Adsorption in Zr-Based MOFs: Comparison and Critical Evaluation of Force Fields

Methane Adsorption in Zr-Based MOFs: Comparison and Critical Evaluation of Force Fields

The right isotherms for the right reasons? Validation of generic force fields for prediction of methane adsorption in metal-organic frameworks

A computational study of the interaction of C2 hydrocarbons with CuBTC

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