Vibrational spectroscopic and quantum theoretical study of host-guest interactions in clathrates: I. Hofmann type clathrates

Hofmann type clatharates are host-guest compounds with the general formula M(NH3)2M’(CN)4.2G, in whichM(NH3)2M’(CN)4 is the host lattice and G is benzene, the guest molecule. In previous studies, host-guest interactions have been investigated by analyzing the RT and LNT vibrational (infrared, far infrared and Raman) spectra of these clathrates. All the observed changes in the vibrational spectra of these clathrates are referred to a host-guest interaction originating fromweakhydrogenbondingbetween the ammonia hydrogen atoms from the host lattice and the π electron cloud of the guest (benzene) molecules. In order to obtain an insight into the relative importance of the local crystalline field vs. the anharmonicity effects on the spectroscopic properties of the guest species upon enclathration, as well as to explain the observed band shifts and splittings, several quantum theoretical approaches are proposed.