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

The piezoelectric
properties of 2-methyl-4-nitroaniline crystals
were explored qualitatively and quantitatively using an electrostatically
embedded many-body (EE-MB) expansion 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 suggest 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.