The Effect of Polarization on Multiple Hydrogen-Bond Formation in Models of Self-Assembling Materials

作者：Chen Yung Fou^*; Dannenberg J J

来源：Journal of Computational Chemistry, 2011, 32(13): 2890-2895.

DOI：10.1002/jcc.21870

• hydrogen-bond
• polarization
• self-assembly
• materials

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 center dot center dot center dot 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.

• 出版日期2011-10