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A Theoretical Study of the Cyclization Processes of Energized CCCSi and CCCP
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A Theoretical Study of the Cyclization Processes of Energized CCCSi and CCCP

M J Maclean, P C H Eichinger, Tianfang Wang, M Fitzgerald and J H Bowie
Journal of Physical Chemistry Part A, Vol.112(49), pp.12714-12720
2008
url
https://doi.org/10.1021/jp807403sView
Published Version

Abstract

Calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31+G(d) level of theory have shown that cyclization of both the ground state triplet and the corresponding singlet state of CCCSi may rearrange to give cyclic isomers which upon ring opening may reform linear C3Si isomers in which the carbon atoms are scrambled. The cyclization processes are energetically favorable with barriers to the transition states from 13 to 16 kcal mol-1. This should be contrasted with the analogous process of triplet CCCC to triplet rhombic C4, which requires an excess energy of 25.8 kcal mol-1. A similar cyclization of doublet CCCP requires 50.4 kcal mol-1 of excess energy; this should be contrasted with the same process for CCCN, which requires 54.7 kcal mol-1 to effect cyclization.

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Chemistry, Physical
Physics, Atomic, Molecular & Chemical
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