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RESEARCH PRODUCT
Semiconducting Clathrates Meet Gas Hydrates: Xe24[Sn136]
Antti J. KarttunenAntti J. KarttunenThomas F. Fässlersubject
Chemistrybusiness.industryOrganic ChemistryClathrate hydrateeducationNoble gasGeneral ChemistryCatalysisSemiconductorAdsorptionChemical physicsComputational chemistryAb initio quantum chemistry methodsAtomNoble gas configurationbusinessPorosityta116description
Semiconducting Group 14 clathrates are inorganic host–guest materials with a close structural relationship to gas hydrates. Here we utilize this inherent structural relationship to derive a new class of porous semiconductor materials: noble gas filled Group 14 clathrates (Ngx[M136], Ng=Ar, Kr, Xe and M=Si, Ge, Sn). We have carried out high-level quantum chemical studies using periodic Local-MP2 (LMP2) and dispersion-corrected density functional methods (DFT-B3LYP-D3) to properly describe the dispersive host–guest interactions. The adsorption of noble gas atoms within clathrate-II framework turned out to be energetically clearly favorable for several host–guest systems. For the energetically most favorable noble gas filled clathrate, Xe24[Sn136], the adsorption energy is −52 kJ mol−1 per guest atom at the LMP2/TZVPP level of theory, corresponding to −9.2 kJ mol−1 per framework Sn atom. Considering that a hypothetical guest-free Sn clathrate-II host framework is only 2.6 kJ mol−1 per Sn atom less stable than diamond-like α-Sn, the stabilization resulting from the noble gas adsorption is very significant.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2014-04-30 |