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Semiconducting Clathrates Meet Gas Hydrates: Xe 24 [Sn 136 ]
Author(s) -
Karttunen Antti J.,
Fässler Thomas F.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402251
Subject(s) - clathrate hydrate , noble gas , adsorption , atom (system on chip) , diamond , xenon , density functional theory , semiconductor , chemistry , quantum chemical , crystallography , molecule , materials science , chemical physics , computational chemistry , hydrate , organic chemistry , optoelectronics , computer science , embedded system
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 (Ng x [M 136 ], 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, Xe 24 [Sn 136 ], 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.