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Density functional theory study of interactions between carbon dioxide and functionalized polyhedral oligomeric silsesquioxanes
Author(s) -
Tezsevin Ilker,
Demirtas Cansu,
Onal Isik,
Dilek Cerag
Publication year - 2017
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25397
Subject(s) - silsesquioxane , density functional theory , chemistry , molecule , intermolecular force , hydrogen bond , supercritical fluid , crystallography , atom (system on chip) , supercritical carbon dioxide , lewis acids and bases , computational chemistry , polymer , organic chemistry , catalysis , computer science , embedded system
Polyhedral Oligomeric Silsesquioxanes (POSS) are cage‐structured inorganic–organic hybrid materials which can be used in various industrial applications. It is recently discovered that POSS structures with certain functional groups can be solubilized in supercritical CO 2 allowing their applications in environmentally benign supercritical processing of materials. In this theoretical study, nature and energetics of the interactions of octatrifluoropropyl POSS, octatrifluoromethyl POSS, and octamethyl POSS with CO 2 are investigated according to the principles of density functional theory (DFT) by use of Gaussian 09 software. Simulations show that CO 2 ‐octamethyl POSS pair has hydrogen bonding between the O atom of CO 2 and the H atom of the methyl group, and CO 2 ‐octatrifluoromethyl POSS pair has interactions between the C atom of CO 2 and the F atom of the trifluoromethyl group. CO 2 ‐octatrifluoropropyl POSS pair is found to have both interaction types. The octamethyl, the octatrifluoromethyl and the octatrifluoropropyl POSS structures have interaction energies of −2.18 kcal/mol, −3.10 kcal/mol, and −3.77 kcal/mol, respectively. This shows that the presence of Lewis acid–Lewis base interaction between C and F instead of hydrogen bonding between O and H atoms enhances the interaction of the molecule with CO 2 , while the presence of both interactions between the octatrifluoropropyl POSS‐CO 2 pair makes the intermolecular interaction even stronger.