When Quantum Fluctuations Meet Structural Instabilities: The Isotope- and Pressure-Induced Phase Transition in the Quantum Paraelectric NaOH

Anhydrous sodium hydroxide, a common and structurally simple compound, shows spectacular isotope effects: NaOD undergoes a first-order transition, which is absent in NaOH. By combining ab initio electronic structure calculations with Feynman path integrals, we show that NaOH is an unusual example of a quantum paraelectric: zero-point quantum fluctuations stretch the weak hydrogen bonds (HBs) into a region where they are unstable and break. By strengthening the HBs via isotope substitution or applied pressure, the system can be driven to a broken-symmetry antiferroelectric phase. In passing, we provide a simple quantitative criterion for HB breaking in layered crystals and show that nuclear quantum effects are crucial in paraelectric to ferroelectric transitions in hydrogen-bonded hydroxides.