Deuteration removes quantum dipolar defects from KDP crystals

Abstract Dielectric properties of the hydrogen-bonded ferroelectric crystal KH 2 PO 4 (KDP) differ significantly from those of KD 2 PO 4 (DKDP). It is well established that deuteration affects the interplay of hydrogen-bond switches and heavy ion displacements that underlie the emergence of macroscopic polarization, but a detailed microscopic model is missing. We show that all-atom path integral molecular dynamics simulations can predict the isotope effects, revealing the microscopic mechanism that differentiates KDP and DKDP. Proton tunneling generates phosphate configurations that do not contribute to the polarization. At low temperatures, these quantum dipolar defects are substantial in KDP but negligible in DKDP. These intrinsic defects explain why KDP has lower spontaneous polarization and transition entropy than DKDP. The prominent role of quantum fluctuations in KDP is related to the unusual strength of the hydrogen bonds and should be equally important in other crystals of the KDP family, which exhibit similar isotope effects.