caa a22 4500 605487480 CHVBK 20210128100451.0 cr unu---uuuuu 210128e20150701xx s 000 0 eng 10.1007/s00214-015-1692-9 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1692-9 CO adsorption complexes in zeolites: How does the inclusion of dispersion interactions affect predictions made from DFT calculations? The case of Na-CHA [Elektronische Daten] [Michael Fischer, Montserrat Delgado, Carlos Areán, Clara Duran] Density functional theory (DFT) calculations have played a pivotal role in identifying and understanding different coordination modes of carbon monoxide adsorbed in zeolites: Previous studies combining IR spectroscopic measurements and DFT have firmly established that an adsorbed CO molecule can interact either with a single cation (single-site interaction), or with two or more cations simultaneously (dual-site or multiple-site interaction). However, one aspect that has been scarcely addressed so far is the dependence of the DFT equilibrium structures on the choice of the functional. With the ongoing development of DFT, exemplified by the more widespread use of dispersion-corrected DFT, this question becomes increasingly relevant. The present study investigates whether the inclusion of an empirical dispersion correction leads to qualitatively different predictions in comparison with dispersion-uncorrected DFT, taking CO adsorbed in sodium-exchanged chabazite having two different Si/Al ratios (Si/Al=11:1 and Si/Al=2:1) as a model system. Equilibrium structures obtained with the PBE functional and with the dispersion-corrected PBE-D functional are compared, revealing a tendency of dispersion-corrected DFT to favour a stronger interaction of CO with dual sites. This is indicated by a short contact between the oxygen atom of the CO molecule (already coordinated through its carbon atom to a primary Na+ cation) and a secondary Na+ cation. In addition to these qualitative findings, the quantitative agreement of calculated adsorption enthalpies and C-O stretching frequencies with experimental values obtained from variable-temperature IR spectroscopy is evaluated. While neither functional is particularly successful in predicting accurate adsorption enthalpies, the range of C-O stretching frequency values delivered by the PBE-D functional shows a better agreement with the experimental measurements. Springer-Verlag Berlin Heidelberg, 2015 Density functional theory nationallicence Dispersion correction nationallicence Zeolites nationallicence Adsorption nationallicence Carbon monoxide nationallicence VTIR spectroscopy nationallicence Fischer Michael Crystallography Group, Department of Geosciences, University of Bremen, Klagenfurter Straße 2, 28359, Bremen, Germany aut Delgado Montserrat Department of Chemistry, University of the Balearic Islands, Cra. Valldemossa, km 7.5, 07122, Palma de Mallorca, Balearic Islands, Spain aut Areán Carlos Department of Chemistry, University of the Balearic Islands, Cra. Valldemossa, km 7.5, 07122, Palma de Mallorca, Balearic Islands, Spain aut Duran Clara Department of Chemistry, University of the Balearic Islands, Cra. Valldemossa, km 7.5, 07122, Palma de Mallorca, Balearic Islands, Spain aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/7(2015-07-01), 1-18 1432-881X 134:7<1 2015 134 214 https://doi.org/10.1007/s00214-015-1692-9 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1692-9 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Fischer Michael Crystallography Group, Department of Geosciences, University of Bremen, Klagenfurter Straße 2, 28359, Bremen, Germany aut NATIONALLICENCE 700 1- Delgado Montserrat Department of Chemistry, University of the Balearic Islands, Cra. Valldemossa, km 7.5, 07122, Palma de Mallorca, Balearic Islands, Spain aut NATIONALLICENCE 700 1- Areán Carlos Department of Chemistry, University of the Balearic Islands, Cra. Valldemossa, km 7.5, 07122, Palma de Mallorca, Balearic Islands, Spain aut NATIONALLICENCE 700 1- Duran Clara Department of Chemistry, University of the Balearic Islands, Cra. Valldemossa, km 7.5, 07122, Palma de Mallorca, Balearic Islands, Spain aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/7(2015-07-01), 1-18 1432-881X 134:7<1 2015 134 214