Crystalline KOH undergoes an antiferroelectric (AFE) proton ordering phase transition at low temperatures, which results in a monoclinic bilayer structure held together by a network of weak hydrogen bonds (HBs). The Curie temperature shifts up when the compound is deuterated, an effect that classical MD is not able to catch. For deeper insights into the transition mechanism, we carry out ab initio MD simulations of KOH and KOD crystals by including quantum effects on the nuclei through Feynman path integrals. The geometric isotope effect and the evolution of the lattice parameters with temperature agree with the experimental data, while the purely classical description is not appropriate. Our results show that deuteration strengthens the HBs in the low-T AFE ordered phase. The transition is characterized by the flipping of OH/OD groups along a bending mode. Above the transition, the system is driven into a dynamical disordered paraelectric phase.

Thermal and Nuclear Quantum Effects at the Antiferroelectric to Paraelectric Phase Transition in {KOH} and {KOD} Crystals / E. Fallacara, P. Depondt, S. Huppert, M. Ceotto, F. Finocchi. - In: JOURNAL OF PHYSICAL CHEMISTRY. C. - ISSN 1932-7447. - 40(2021 Sep 24), pp. 22328-22334. [10.1021/acs.jpcc.1c06953]

Thermal and Nuclear Quantum Effects at the Antiferroelectric to Paraelectric Phase Transition in {KOH} and {KOD} Crystals

M. Ceotto
Penultimo
;
2021

Abstract

Crystalline KOH undergoes an antiferroelectric (AFE) proton ordering phase transition at low temperatures, which results in a monoclinic bilayer structure held together by a network of weak hydrogen bonds (HBs). The Curie temperature shifts up when the compound is deuterated, an effect that classical MD is not able to catch. For deeper insights into the transition mechanism, we carry out ab initio MD simulations of KOH and KOD crystals by including quantum effects on the nuclei through Feynman path integrals. The geometric isotope effect and the evolution of the lattice parameters with temperature agree with the experimental data, while the purely classical description is not appropriate. Our results show that deuteration strengthens the HBs in the low-T AFE ordered phase. The transition is characterized by the flipping of OH/OD groups along a bending mode. Above the transition, the system is driven into a dynamical disordered paraelectric phase.
Settore CHIM/02 - Chimica Fisica
Divide and Conquer ad initio semiclassical molecular dynamics for spectropic calculations of complex systems (SEMICOMPLEX)
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/872393
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