caa a22 4500 605487960 CHVBK 20210128100453.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s00214-015-1642-6 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1642-6 A density functional theory study on the interaction of paraffins, olefins, and acetylenes with Na-ETS-10 [Elektronische Daten] [Renjith Pillai, Miguel Jorge, José Gomes] High demand for economically viable separation processes such as adsorptive separation for mixtures of hydrocarbons drives the need for understanding the interaction of hydrocarbons with titanosilicate adsorbents, to replace the energy-intensive cryogenic hydrocarbon separation. Density functional theory (DFT) was used to optimize the geometries and calculate the enthalpies for the interactions between paraffins (C2H6, C3H8), olefins (C2H4, C3H6), and acetylenes (C2H2, C3H4) with a cluster model of the Engelhard titanosilicate having sodium extra-framework cations (Na-ETS-10). The DFT calculations were performed with the M06-L exchange correlation functional and were corrected for the basis set superposition error with the counterpoise method. The calculated enthalpies for the interaction of hydrocarbons with Na-ETS-10 decrease with the decrease in the number of carbon atoms, in the order acetylenes>olefins>paraffins, and compare well with experimental data available in the literature. The enthalpies calculated at the M06-L/6-31++G** level of theory for the two extreme cases, i.e., strongest and weakest interactions, are −62.8kJmol−1 (C3H4) and −26.9kJmol−1 (C2H6). Additionally, the calculated vibrational frequencies are in good agreement with the characteristic vibrational modes of ETS-10 and of the interactions of hydrocarbons with Na+ in the 12-membered channel in ETS-10. Springer-Verlag Berlin Heidelberg, 2015 ETS-10 nationallicence Sorption nationallicence Separation nationallicence Hydrocarbons nationallicence DFT calculations nationallicence Pillai Renjith CICECO, Departamento de Química, Universidade de Aveiro, Campus Universitário de Santiago, 3810-193, Aveiro, Portugal aut Jorge Miguel Department of Chemical and Process Engineering, University of Strathclyde, 75 Montrose Street, G1 1XJ, Glasgow, UK aut Gomes José CICECO, Departamento de Química, Universidade de Aveiro, Campus Universitário de Santiago, 3810-193, Aveiro, Portugal aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/4(2015-04-01), 1-12 1432-881X 134:4<1 2015 134 214 https://doi.org/10.1007/s00214-015-1642-6 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/s00214-015-1642-6 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Pillai Renjith CICECO, Departamento de Química, Universidade de Aveiro, Campus Universitário de Santiago, 3810-193, Aveiro, Portugal aut NATIONALLICENCE 700 1- Jorge Miguel Department of Chemical and Process Engineering, University of Strathclyde, 75 Montrose Street, G1 1XJ, Glasgow, UK aut NATIONALLICENCE 700 1- Gomes José CICECO, Departamento de Química, Universidade de Aveiro, Campus Universitário de Santiago, 3810-193, Aveiro, Portugal aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/4(2015-04-01), 1-12 1432-881X 134:4<1 2015 134 214