A Computational Characterization of CH<sub>4</sub>@C<sub>60</sub>
The recently synthetically prepared endohedral CH<sub>4</sub>@C<sub>60</sub> was characterized here using calculations—namely its structure, energetics, thermodynamics, and vibrational spectrum. The calculations were carried out with DFT (density-functional theory) methods, n...
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MDPI AG
2024-02-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/12/3/64 |
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| author | Zdeněk Slanina Filip Uhlík Takeshi Akasaka Xing Lu Ludwik Adamowicz |
| author_facet | Zdeněk Slanina Filip Uhlík Takeshi Akasaka Xing Lu Ludwik Adamowicz |
| author_sort | Zdeněk Slanina |
| collection | DOAJ |
| description | The recently synthetically prepared endohedral CH<sub>4</sub>@C<sub>60</sub> was characterized here using calculations—namely its structure, energetics, thermodynamics, and vibrational spectrum. The calculations were carried out with DFT (density-functional theory) methods, namely by the DFT M06-2X functional and MP2, as well as B2PLYPD advanced correlated, treatments with the standard 6-31++G** and 6-311++G** basis sets, corrected for the basis set superposition error evaluated using the approximative Boys–Bernardi counterpoise method. The symmetry of the endohedral obtained in the geometry optimizations was tetrahedral T. The energetics of CH<sub>4</sub> encapsulation into C<sub>60</sub> was attractive (i.e., with a negative encapsulation-energy term), producing a substantial energy gain of −13.94 kcal/mol at the most advanced computational level, B2PLYPD/6-311++G**. The encapsulation equilibrium constants for CH<sub>4</sub>@C<sub>60</sub> were somewhat higher than previously found with the CO@C<sub>60</sub> system. For example at 500 K, the encapsulation equilibrium constant for CH<sub>4</sub>@C<sub>60</sub> had a value one order of magnitude larger than for CO@C<sub>60</sub>. The encapsulation thermodynamic characteristics suggest that high-pressure and high-temperature synthesis could in principle also be possible for CH<sub>4</sub>@C<sub>60</sub>. |
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| last_indexed | 2024-04-24T18:10:35Z |
| publishDate | 2024-02-01 |
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| series | Inorganics |
| spelling | doaj.art-ba4127df2fa94852bc094c207c7b78302024-03-27T13:47:04ZengMDPI AGInorganics2304-67402024-02-011236410.3390/inorganics12030064A Computational Characterization of CH<sub>4</sub>@C<sub>60</sub>Zdeněk Slanina0Filip Uhlík1Takeshi Akasaka2Xing Lu3Ludwik Adamowicz4Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ 85721-0041, USADepartment of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Albertov 6, 128 43 Praha 2, Czech RepublicState Key Laboratory of Materials Processing and Die & Mould Technology, School of Material, Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, ChinaState Key Laboratory of Materials Processing and Die & Mould Technology, School of Material, Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, ChinaDepartment of Chemistry and Biochemistry, University of Arizona, Tucson, AZ 85721-0041, USAThe recently synthetically prepared endohedral CH<sub>4</sub>@C<sub>60</sub> was characterized here using calculations—namely its structure, energetics, thermodynamics, and vibrational spectrum. The calculations were carried out with DFT (density-functional theory) methods, namely by the DFT M06-2X functional and MP2, as well as B2PLYPD advanced correlated, treatments with the standard 6-31++G** and 6-311++G** basis sets, corrected for the basis set superposition error evaluated using the approximative Boys–Bernardi counterpoise method. The symmetry of the endohedral obtained in the geometry optimizations was tetrahedral T. The energetics of CH<sub>4</sub> encapsulation into C<sub>60</sub> was attractive (i.e., with a negative encapsulation-energy term), producing a substantial energy gain of −13.94 kcal/mol at the most advanced computational level, B2PLYPD/6-311++G**. The encapsulation equilibrium constants for CH<sub>4</sub>@C<sub>60</sub> were somewhat higher than previously found with the CO@C<sub>60</sub> system. For example at 500 K, the encapsulation equilibrium constant for CH<sub>4</sub>@C<sub>60</sub> had a value one order of magnitude larger than for CO@C<sub>60</sub>. The encapsulation thermodynamic characteristics suggest that high-pressure and high-temperature synthesis could in principle also be possible for CH<sub>4</sub>@C<sub>60</sub>.https://www.mdpi.com/2304-6740/12/3/64metallic and non-metallic endohedralsfullerene encapsulationstability calculationstheory–experiment comparison |
| spellingShingle | Zdeněk Slanina Filip Uhlík Takeshi Akasaka Xing Lu Ludwik Adamowicz A Computational Characterization of CH<sub>4</sub>@C<sub>60</sub> Inorganics metallic and non-metallic endohedrals fullerene encapsulation stability calculations theory–experiment comparison |
| title | A Computational Characterization of CH<sub>4</sub>@C<sub>60</sub> |
| title_full | A Computational Characterization of CH<sub>4</sub>@C<sub>60</sub> |
| title_fullStr | A Computational Characterization of CH<sub>4</sub>@C<sub>60</sub> |
| title_full_unstemmed | A Computational Characterization of CH<sub>4</sub>@C<sub>60</sub> |
| title_short | A Computational Characterization of CH<sub>4</sub>@C<sub>60</sub> |
| title_sort | computational characterization of ch sub 4 sub c sub 60 sub |
| topic | metallic and non-metallic endohedrals fullerene encapsulation stability calculations theory–experiment comparison |
| url | https://www.mdpi.com/2304-6740/12/3/64 |
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