Nature and physical origin of CH/π interaction: Significant difference from conventional hydrogen bonds

Seiji Tsuzuki, Asuka Fujii

Research output: Contribution to journalArticlepeer-review

268 Citations (Scopus)


Recently reported high-level ab initio calculations and gas phase spectroscopic measurements show that the nature of CH/π interactions is considerably different from conventional hydrogen bonds, although the CH/π interactions were often regarded as the weakest class of hydrogen bonds. The major source of attraction in the CH/π interaction is the dispersion interaction and the electrostatic contribution is small, while the electrostatic interaction is mainly responsible for the attraction in the conventional hydrogen bonds. The nature of the "typical" CH/π interactions is similar to that of van der Waals interactions, if some exceptional "activated" CH/π interactions of highly acidic C-H bonds are excluded. Shifts of C-H vibrational frequencies and electronic spectra also support the similarity. The hydrogen bond is important in controlling structures of molecular assemblies, since the hydrogen bond is sufficiently strong and directional due to the large electrostatic contribution. On the other hand, the directionality of the "typical" CH/π interaction is very weak. Although the "typical" CH/π interaction is often regarded as an important interaction in controlling the structures of molecular assemblies as in the cases of conventional hydrogen bonds, the importance of the "typical" CH/π interactions is questionable.

Original languageEnglish
Pages (from-to)2584-2594
Number of pages11
JournalPhysical Chemistry Chemical Physics
Issue number19
Publication statusPublished - 2008
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry


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