ABSTRACT

Accurate ab initio description of the adsorbate-adsorbent inter-

actions in MOFs containing coordinatively unsaturated transition

metal sites represents a significant challenge for computational

chemists. The following complications are often faced: (i) spin

coupling between the unpaired electrons on individual transition

metal ions, (ii) complicated electronic structure of individual tran-

sition metal ions or metal-oxo-clusters resulting in multireference

character of corresponding wavefunction, and (iii) the importance

of dispersion interaction between adsorbate and adsorbent. As

a consequence, a reliability of computational methods based on

popular density functional theory (DFT) is often insufficient.

The suitability, reliability, and accuracy of DFT methods for the

description of adsorption in MOFs are discussed in this chapter

on the basis of the comparison with highly accurate wavefunction-

based methods and with accurate experimental data.