The singlet and triplet states of phenyl cation. A hybrid approach for locating minimum energy crossing points between non-interacting potential energy surfaces
 Harvey, Jeremy N.^a; Aschi, Massimiliano^a; Schwarz, Helmut^a; Koch, Wolfram^a

: a. Institut für Organische Chemie der Technischen Universität Berlin, Strasse des 17. Juni 135, D-10623 Berlin, Germany,

 Keywords: Key words: Phenyl cation; Minimum energy crossing points

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Abstract.

The phenyl cation is known to have two low-energy minima, corresponding to ¹ A ₁ and ³ B ₁ states, the first of which is more stable by ca. 25 kcal/mol. The minimum energy crossing point between these two surfaces, located at various levels including a hybrid method first described here, lies just above the minimum of the triplet, 0.12 kcal/mol at the CCSD(T)/cc-pVDZ//B3LYP/SV level, and there is significant spin-orbit coupling between the surfaces at this point. On the basis of these results, the lifetime of the triplet is expected to be very short.

Publisher: Springer-Verlag, Berlin/Heidelberg