Molecular Mechanism of Swing Effect in Zeolitic Imidazolate Framework ZIF‐8: Continuous Deformation upon Adsorption

Zeolitic imidazolate framework ZIF‐8 displays flexibility of its structure by rotation of its imidazolate linker. This “swing effect” has been widely described in the literature, both experimentally and theoretically, as a bistable system where the linker oscillates between two structures: “open win...

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Bibliographic Details
Published in:Chemphyschem 2017-10, Vol.18 (19), p.2732-2738
Main Author: Coudert, François‐Xavier
Format: Article
Language:English
Subjects:
Adsorption
Chemical Sciences
Deformation effects
Deformation mechanisms
first-principles simulations
Flexibility
Material chemistry
Metal-organic frameworks
Molecular dynamics
or physical chemistry
Quantum chemistry
Stepped
Theoretical and
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Summary:Zeolitic imidazolate framework ZIF‐8 displays flexibility of its structure by rotation of its imidazolate linker. This “swing effect” has been widely described in the literature, both experimentally and theoretically, as a bistable system where the linker oscillates between two structures: “open window” and “closed window”. By using quantum chemistry calculations and first‐principles molecular dynamics simulations, it is shown that the deformation upon adsorption is in fact continuous upon pore loading, with thermodynamics of packing effects being the reason behind stepped adsorption isotherms experimentally observed. Finally, we study a variant of ZIF‐8 with a different linker, highlighting the influence of the linker and the balance of microscopic interactions on the framework's flexibility. The flexibility of zeolitic imidazolate framework ZIF‐8 and its “swing” effect are investigated by first‐principles molecular dynamics.
ISSN:1439-4235
1439-7641
DOI:10.1002/cphc.201700463