Predicting adsorption enthalpies on silicalite and HZSM-5 : a benchmark study on DFT strategies addressing dispersion interactions

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Predicting adsorption enthalpies on silicalite and HZSM-5 : a benchmark study on DFT strategies addressing dispersion interactions
Title:
Predicting adsorption enthalpies on silicalite and HZSM-5 : a benchmark study on DFT strategies addressing dispersion interactions
Journal Title:
Journal of Computational Chemistry
Keywords:
Publication Date:
18 February 2014
Citation:
Chiu, C.-C.; Vayssilov, G. N.; Genest, A.; Borgna, A.; Rösch, N., Predicting adsorption enthalpies on silicalite and HZSM-5 : a benchmark study on DFT strategies addressing dispersion interactions. Journal of Computational Chemistry 2014, 35, (10), p 809-819.
Abstract:
We evaluated the accuracy of periodic density functional calculations for adsorption enthalpies of water, alkanes, and alcohols in silicalite and HZSM‐5 zeolites using a gradient‐corrected density functional with empirical dispersion corrections (PBE‐D) as well as a nonlocal correlation functional (vdW‐DF2). Results of both approaches agree in acceptable fashion with experimental adsorption energies of alcohols in silicalite, but the adsorption energies for n ‐alkanes in both zeolite models are overestimated, by 21−46 kJ mol−1. For PBE‐D calculations, the adsorption of alkanes is exclusively determined by the empirical dispersion term, while the generalized gradient approximation‐DFT part is purely repulsive, preventing the molecule to come too close to the zeolite walls. The vdW‐DF2 results are comparable to those of PBE‐D calculations, but the latter values are slightly closer to the experiment in most cases. Thus, both computational approaches are unable to reproduce available experimental adsorption energies of alkanes in silicalite and HZSM‐5 zeolite with chemical accuracy.
License type:
PublisherCopyrights
Funding Info:
This work was supported by Leibniz Rechenzentrum Munchen, International Graduate School of Science and Engineering at Technische Universitat Munchen, A*Star Research Attachment Program (ARAP) scholarship of the A*STAR Graduate Academy and FP7 project Beyond Everest.
Description:
This is the peer reviewed version of the following article: Chiu, C.-C.; Vayssilov, G. N.; Genest, A.; Borgna, A.; Rösch, N., Predicting adsorption enthalpies on silicalite and HZSM-5 : a benchmark study on DFT strategies addressing dispersion interactions. Journal of Computational Chemistry 2014, 35, (10), p 809-819, which has been published in final form at https://doi.org/10.1002/jcc.23558. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
ISSN:
0192-8651
1096-987X
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