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Fullerene Thermochemical Stability: Accurate Heats of Formation for Small Fullerenes, the Importance of Structural Deformation on Reactivity, and the Special Stability of C60
- Source :
- The Journal of Physical Chemistry A. 124(33):6688-6698
- Publication Year :
- 2020
- Publisher :
- American Chemical Society, 2020.
-
Abstract
- We have used quantum chemistry computations, in conjunction with isodesmic-type reactions, to obtain accurate heats of formation (HoFs) for the small fullerenes C20 (2358.2 ± 8.0 kJ mol-1), C24 (2566.2 ± 7.6), and the lowest-energy isomers of C32 (2461.1 ± 15.4), C42 (2629.0 ± 20.5), and C54 (2686.2 ± 25.3). As part of this endeavor, we have also obtained accurate HoFs for several medium-sized molecules, namely 216.6 ± 1.4 for fulvene, 375.5 ± 1.5 for pentalene, 670.8 ± 2.9 for acepentalene, and 262.7 ± 2.5 for acenaphthylene. We combine the energies of the small fullerenes and previously obtained energies for larger fullerenes (from C60 to C6000) into a full picture of fullerene thermochemical stability. In general, the per-carbon energies can be reasonably approximated by the "R+D"model that we have previously developed [ Chan et al. J. Chem. Theory Comput. 2019, 15, 1255-1264 ], which takes into account Resonance and structural Deformation factors. In a case study on C54, we find that most of the high-deformation-energy atoms correspond to the sites of the C-Cl bond in the experimentally captured C54Cl8.In another case study, we find that C60 has the lowest value for the maximum local-deformation energy when compared with similar-sized fullerenes, which is consistent with its "special stability". These results are indicative of structural deformation playing an important role in the reactivity of fullerenes.<br />The journal of physical chemistry. A, 124(33), pp.6688-6698; 2020
- Subjects :
- Fullerene
010304 chemical physics
Chemistry
Thermodynamics
010402 general chemistry
01 natural sciences
Quantum chemistry
Stability (probability)
Standard enthalpy of formation
0104 chemical sciences
0103 physical sciences
Reactivity (chemistry)
Structural deformation
Physical and Theoretical Chemistry
Subjects
Details
- Language :
- English
- ISSN :
- 10895639
- Volume :
- 124
- Issue :
- 33
- Database :
- OpenAIRE
- Journal :
- The Journal of Physical Chemistry A
- Accession number :
- edsair.doi.dedup.....e91d58b25b63aab11a469c5f6c7a7570