Pseudorotation of the Benzene Radical Cation Associated with HCN or CH3CN Molecules

Abstract

for the first time the question is raised concerning the effect of ion-molecular associations on the structural flexibility of radical ions of aromatic compounds with respect to pseudorotation. It is shown within the DFT method that the complex structure of the potential energy surface and structural flexibility of the Jahn-Teller benzene cation are preserved during the formation of complexes with a hydrogen cyanide or acetonitrile molecule. The pseudorotation barrier of the radical cation in considered complexes depends on the relative orientation of particles and varies from 0.1 kcal/mol to ∼2 kcal/mol.