The effect of polarization on multiple hydrogen-bond formation in models of self-assembling materials

✍ Scribed by Yung-Fou Chen; J. J. Dannenberg

• Publisher: John Wiley and Sons
• Year: 2011
• Tongue: English
• Weight: 231 KB
• Volume: 32
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.21870

✦ Synopsis

Abstract

We report density functional theory calculations at the B3LYP/D95(d,p) level on several different cyclic H‐bonding dimers, where the monomers of each are connected by a pair of NH**···**OC H‐bonding interactions, and the H‐bonding donors and acceptors on each monomer are separated by polarizable spacers. Depending on the structures, the individual H‐bonds vary in strength (enthalpy) by over a factor of four, from 2.41 to 10.99 kcal/mol. We attribute most of the variation in interaction energies to differences in the extent of polarization due to each of the H‐bonds, which can either combine constructively or destructively. The dipole–dipole interactions between the pair of H‐bonds also contribute somewhat to the relative stabilities. The relevance of these results to the design of self‐assembling materials is discussed. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011