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+ cations and the transition state for their interconversion to optimization and frequency calculations at the QCSID/6-31G* level followed by single-point calculations at the CCSD(T)/cc-pVTZ level. On inclusion of ZPE differences, the cyclobutonium cation is less stable than the cyclopropylcarbinyl cation by 0.1 kcal/mol, while the activation enthalpy (starting from the latter cation) is 0.62 kcal/mol. (On a 298 K enthalpy scale, the transition state falls 0.22 kcal/mol below the cyclopropylcarbinyl cation!) Thus, at this level of theory, the system must be regarded as extremely fluxional, perhaps nonclassical, in the gas phase.
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These values are not unreasonable: they correspond to the electrostatic attraction between two point charges of 0.7 at a distance of ca. 4.3 Å which is not far from the distance of the Cl atom from the center of charge of the cationic hydrocarbon moieties in the two ion pair complexes.
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