Properties of CO adsorbed in ZSM5 zeolite: Density functional theory study using the embedding scheme based on electron density partitioning

The CO molecule is frequently used as a probe in studies of zeolites where it adsorbs on metal cations. Compared with the free CO molecule, the stretching frequency of CO adsorbed in a zeolite is blue-shifted. The magnitude of the shift depends on the cation. The theoretical studies by Ferrari et al. [J. Chem. Phys., 105, 4129 (1996)] show that the isolated cation does not provide a good model of the zeolite because the calculated shifts are significantly overestimated. In this work, the effects of the interactions between the ${\mathrm{Me}}^{\mathrm{+}}\mathrm{CO}$ $(\mathrm{Me=Li},$ Na, or K) complex and the zeolite framework on the properties of CO adsorbed on the cation site are investigated. The properties of the investigated complexes are studied using the embedded molecule approach applying the orbital-free effective embedding potential derived within the subsystem formulation of density functional theory. In order to identify the major microsopic effects affecting the properties of the bound probe molecule, a hierarchy of cluster models is used to represent the zeolite framework. For the largest cluster model applied, the calculated frequency shifts agree within few ${\mathrm{cm}}^{\mathrm{-1}}$ with experimental data.