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Adsorption in zeolites using mechanically embedded ONIOM clusters [electronic resource].

Published:
Washington, D.C. : United States. Dept. of Energy. Office of Basic Energy Sciences, 2016.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
Physical Description:
pages 26,094-26,106 : digital, PDF file
Additional Creators:
United States. Department of Energy. Office of Basic Energy Sciences and United States. Department of Energy. Office of Scientific and Technical Information
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Summary:
Here, we have explored mechanically embedded three-layer QM/QM/MM ONIOM models for computational studies of binding in Al-substituted zeolites. In all the models considered, the high-level-theory layer consists of the adsorbate molecule and of the framework atoms within the first two coordination spheres of the Al atom and is treated at the M06-2X/6-311G(2df,p) level. For simplicity, flexibility and routine applicability, the outer, low-level-theory layer is treated with the UFF. We have modelled the intermediate-level layer quantum mechanically and investigated the performance of HF theory and of three DFT functionals, B3LYP, M06-2X and ωB97x-D, for different layer sizes and various basis sets, with and without BSSE corrections. We have studied the binding of sixteen probe molecules in H-MFI and compared the computed adsorption enthalpies with published experimental data. We have demonstrated that HF and B3LYP are inadequate for the description of the interactions between the probe molecules and the framework surrounding the metal site of the zeolite on account of their inability to capture dispersion forces. Both M06-2X and ωB97x-D on average converge within ca. 10% of the experimental values. We have further demonstrated transferability of the approach by computing the binding enthalpies of n-alkanes (C1–C8) in H-MFI, H-BEA and H-FAU, with very satisfactory agreement with experiment. The computed entropies of adsorption of n-alkanes in H-MFI are also found to be in good agreement with experimental data. Finally, we compare with published adsorption energies calculated by periodic-DFT for n-C3 to n-C6 alkanes, water and methanol in H-ZSM-5 and find very good agreement.
Report Numbers:
E 1.99:1425201
Subject(s):
Note:
Published through SciTech Connect.
09/01/2016.
Physical Chemistry Chemical Physics. PCCP (Print) 18 37 ISSN 1463-9076; PPCPFQ AM
Ryan E. Patet; Stavros Caratzoulas; Dionisios G. Vlachos.
Univ. of Delaware, Newark, DE (United States)
Funding Information:
SC0001004
View MARC record | catkey: 24043817