Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2011-06-16

Steric and electronic effects in the host-guest hydrogen bonding in clathrate hydrates.

Waldemar Kulig, Piotr Kubisiak, Lukasz Cwiklik

Index: J. Phys. Chem. A 115(23) , 6149-54, (2011)

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Abstract

Clathrate hydrates with polar guest molecules (dimethyl ether, ethylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran) were studied by means of the density functional theory. A model of a large cage of structure-I clathrate was employed. Optimal configurations of encaged guests were investigated with a focus on the host-guest hydrogen bond formation. Weak hydrogen bonds were found to be formed by each guest, while for THP a strong hydrogen bond and formation of L-defect was also observed. This is in accord with previous computational and experimental studies. Steric factors were shown to play a key role for the strength of the hydrogen bond formed. Interestingly, the host-guest binding is influenced not only by the size of a guest molecule but also by its shape. This work demonstrates that both electronic and steric properties of a polar guest should be considered for a full description of clathrate systems.© 2011 American Chemical Society