| Autor: |
Cao, Baopeng, Peres, Tikva, Lifshitz, Chava, Cross, R. James, Saunders, Martin |
| Zdroj: |
Chemistry - A European Journal; March 2006, Vol. 12 Issue: 8 p2213-2221, 9p |
| Abstrakt: |
Unimolecular decomposition of C70+and its endohedral cation N@C70+were studied by high‐resolution mass‐analyzed ion kinetic energy (MIKE) spectrometry. Information on the energetics and dynamics of these reactions was extracted. C70+dissociates unimolecularly by loss of a C2unit, whereas N@C70+expels the endohedral N atom. Kinetic energy release distributions (KERDs) in these reactions were measured. By use of finite heat bath theory (FHBT), the binding energy for C2emission from C70+and the activation energy for N elimination from N@C70+were deduced from KERDs in the light of a recent finding that fragmentation of fullerene cations proceeds via a very loose transition state. The activation energy measured for N extrusion from N@C70+was found to be lower than that for C2evaporation, higher than the value from its neutral molecule N@C70obtained on the basis of thermal stability measurements, and coincident with the theoretical value. The results provide confirmation that the proposed extrusion mechanism in which the N atom escapes from the cage via formation of an aza‐bridged intermediate is correct. |
| Databáze: |
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