The mechanism of ozonolysis on the surface of C70 fullerene. The free energy surface theoretical study
| Autor: | Andrzej Bil |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
Ozonolysis
010405 organic chemistry Chemistry Organic Chemistry Thermal decomposition Metadynamics 010402 general chemistry 01 natural sciences 0104 chemical sciences Analytical Chemistry Inorganic Chemistry chemistry.chemical_compound Criegee intermediate C70 fullerene Potential energy surface Physical chemistry Density functional theory Ground state Spectroscopy |
| Zdroj: | Journal of Molecular Structure. 1185:361-368 |
| ISSN: | 0022-2860 |
| Popis: | Density functional theory based metadynamics simulations of the room temperature ground state free energy surfaces (FES) of a,a-C70O3/a,a-C70O, c,c-C70O3/c,c-C70O, d,d-C70O3/d,d-C70O and e,e-C70O3/e,e-C70O systems have revealed several structures relevant for the thermal decomposition of the experimentally known c,c-C70O3 and hypothetical a,a-C70O3, d,d-C70O3 and e,e-C70O3 ozonides. Criegee intermediate, an open structure with carbonyl oxide and carbonyl groups, plays an important role in the possible mechanism of decomposition of all studied ozonides, while only for e,e-C70O3/e,e-C70O system it is related to the minimum on the underlying FES. The differences between the topography of FES and the previously reported related potential energy surface indicates the influence of a thermal factor on processes on C70 surface. Only c,c-C70O3 should decompose thermally to form c,c-C70O epoxide as the final product while for the other studied ozonides the preferred reaction channel seems to be the one leading to the structures with O2 moiety entrapped over the C C bonds adjacent to the C O C group. Hypothetical oxidoannulene form of c,c-C70O is not related to a clear minimum on the free energy surface. |
| Databáze: | OpenAIRE |
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