CLOPPA analysis of the molecular polarizability and the energy of strong intramolecular hydrogen bonds: resonance assisted?

J Phys Chem A. 2012 Dec 13;116(49):12175-83. doi: 10.1021/jp309612a. Epub 2012 Nov 30.

Abstract

The contributions from localized orbitals within the polarization propagator approach (CLOPPA) method is applied to investigate the influence of the π system on the polarizability of the intramolecular hydrogen bond of malonaldehyde, in order to address if this linear response property provides evidence for the existence of the resonance assisted HB (RAHB) mechanism. On the same grounds, this influence on the energy of the hydrogen bond and the potential energy curve of the proton are also evaluated. Results obtained seem to confirm that the π system delocalizes on the hydrogen bond region, and this effect of delocalization is partially responsible for the unusual strength of this intramolecular hydrogen bond.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Hydrogen Bonding
  • Malondialdehyde / chemistry*
  • Quantum Theory*

Substances

  • Malondialdehyde