Plastic ionic molecular
crystals are a novel class of materials
that have attracted recent interest due to the discovery of ferroelectric
and piezoelectric properties together with an orientationally disordered
mesophase with high plasticity. Despite the growing interest, little
is known about the mechanisms that underpin their piezoelectric properties.
To address this knowledge gap, we use density functional theory calculations
with van der Waals density functionals to study the dielectric, piezoelectric,
and elastic properties of 11 plastic ionic molecular crystals. The
piezoelectric coefficients were found to reach values comparable to
inorganic piezoelectrics. Further, some plastic crystals have strikingly
large piezoelectric anisotropies. For HQReO4 (quinuclidinium
perrhenate) an anisotropy of |d
16/d
33| = 118 was found, 11 times that of LiNbO3, a phase pure inorganic noted for its anisotropy. Our study
links the anisotropy to the rotational motion of the constituent molecules
in response to shear stress. The large shear piezoelectric coefficients,
yet modest dielectric permittivity, results in coupling coefficientsa
measure of its suitability for energy harvestingwith values
up to 0.79. Our study points to the engineering of the rotational
response of plastic ionic crystals as key to realizing the outstanding
functional properties of these compounds.