Cation-pi-anion interaction: a theoretical investigation of the role of induction energies

J Phys Chem A. 2007 Aug 16;111(32):7980-6. doi: 10.1021/jp073337x. Epub 2007 Jul 26.


Cation-pi and the corresponding anion-pi interactions have in general been investigated as binary complexes despite their association with counterions. However, a recent study of the ammonia channel highlights the important but overlooked role of anions in cation-pi interactions. In an effort to examine the structural and energetic consequences of the presence of counterions, we have carried out detailed ab initio calculations on some model cation-pi-anion ternary complexes and evaluated the nonpair potential terms, three-body contributions, and attractive and repulsive energy components of the interaction energy. The presence of the anion in the vicinity of the pi system leads to a large redistribution of electron density and hence leads to an inductive stabilization. The resulting electronic and geometrical changes have important consequences in both chemical and biological systems. Compared to cation-pi-anion ternary complexes, the magnitude of the cation-pi interaction in pi-cation-anion ternary complexes is markedly lower because of charge transfer from the anion to the cation.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anions*
  • Cations*
  • Electrons*
  • Energy Transfer
  • Models, Chemical*
  • Models, Theoretical


  • Anions
  • Cations