Investigations of the bond-selective response in a piezoelectric Li2SO4.H2O crystal to an applied external electric...

Piezoelectric lithium sulfate monohydrate, Li2SO4.H2O, was analyzed with respect to the relationship between the static structural properties of the crystal and its response to an external electric field. The static electron density was determined via standard low-temperature X-ray data collection at 90 (5) K using an Enraf-Nonius CAD-4 diffractometer, Mo Kalpha radiation and multipole model refinement. Then a synchrotron-radiation experiment using the D3 beamline at HASYLAB was conducted in order to investigate the structural deformations in Li2SO4.H2O caused by an applied external electric field. In particular, the shifts of Bragg-peak positions induced by the electric field were measured and the piezoelectric constants d211, d222, d233 and d213 of Li2SO4.H2O were obtained from the shifts. With the same experimental setup the variations of more than 100 Bragg intensities were measured under an applied electric field. The data were used to refine the corresponding displacements of individual atoms within the unit cell. The distortions of the cation-anion bond lengths in the LiO4, LiO3(H2O) and SO4 tetrahedra were evaluated and then analyzed in terms of the electron-density-related properties of the Li-O and S-O bonds. The two lithium structural units were found to be strongly deformed by the applied electric field, while the SO(4) tetrahedron changed less. This is in agreement with the low bond strength of the Li-O bonds.