Piezoelectric Effects of Applied Electric Fields on Hydrogen-Bond Interactions: First-Principles Electronic Structure Investigation of Weak Electrostatic Interactions

Keith A. Werling, Geoffrey R Hutchison, and Daniel S Lambrecht. “Piezoelectric Effects of Applied Electric Fields on Hydrogen-Bond Interactions: First-Principles Electronic Structure Investigation of Weak Electrostatic Interactions” The Journal of Physical Chemistry Letters 2013, 4 (9), pp 1365–1370 Online. The supplemental info is available for download here: Werling SI.

 

Screen Shot 2013-04-09 at 3.47.24 PM The piezoelectric properties of 2-methyl-4-nitroaniline crystals were explored qualitatively and quantitatively using an electrostatically embedded many-body expansion (EE-MB) scheme for the correlation energies of a system of monomers within the crystal. The results demonstrate that hydrogen bonding is an inherently piezoelectric interaction, deforming in response to the electrostatic environment. We obtain piezo-coefficients in excellent agreement with the experimental values. This approach reduces computational cost and reproduces the total Resolution of the Identity (RI)-Møller-Plesset second order perturbation theory (RI-MP2) energy for the system to within 1.3×10-5 %. Furthermore, the results suggest novel ways to self-assemble piezoelectric solids and that accurate treatment of hydrogen bonds requires precise electrostatic evaluation. Considering the ubiquity of hydrogen bonds across chemistry, materials, and biology, a new electromechanical view of these interactions is required.