without changing your settings we'll assume you are happy to receive all RSC cookies.
You can change your cookie settings by navigating to our Privacy and Cookies page and following the instructions. These instructions
are also obtainable from the privacy link at the bottom of any RSC page.
Center for Biomolecules and Complex Molecular Systems, Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, Prague 6, Czech Republic
; Fax: +420-220410320
; Tel: +420-220410324
Phys. Chem. Chem. Phys., 2008,10, 4189-4198
21 Feb 2008,
16 Apr 2008
First published online
29 May 2008
The interaction of acetonitrile with the extra-framework Na+ cations in zeolites, namely Na-LTA and Na-FER, was investigated. The relative stabilities of possible types of adsorption complexes were calculated at the periodic DFT level. Individual effects on the complex stability and on the vibrational dynamics of adsorbed acetonitrile were qualitatively analysed on various cluster models. The acetonitrile primarily interacts with the Na+ cation (via the N end), and the complex stability is modulated by the interaction of the methyl group with the framework oxygen atoms, which has a partial hydrogen-bond character. In line with the results of recent analyses of CO interactions with metal-exchanged zeolites [D. Nachtigallová, O. Bludský, C. O. Areán, R. Bulanek and P. Nachtigall, Phys. Chem. Chem. Phys., 2006, 8, 4849], two types of effects should be taken into consideration for acetonitrile complexes in Na-zeolites: (i) the effects from the bottom, reflecting the accessibility and coordination of the primary metal cation, to which the acetonitrile molecule is bonded via the N atom; and (ii) the effects from the top, including H-bond formation (stabilising effect) or repulsion due to the secondary metal cation. The effect from the bottom results in a blue shift of νCN while the effect from the top (H-bond formation) results in a red shift in both νCN and νCH.
Fetching data from CrossRef. This may take some time to load.
This may take some time to load.
Physical Chemistry Chemical Physics
- Information Point