Observation of Nuclear Quantum Effects and Hydrogen Bond Symmetrisation in High Pressure Ice

Abstract

Hydrogen bond symmetrisations in H-bonded systems triggered by pressure induced nuclear quantum effects (NQEs) is a long-known concept1 but experimental evidences in high-pressure ices have remained elusive with conventional methods2,3. Theoretical works predicted quantum-mechanical tunneling of protons within water ices to occur at pressures above 30 GPa and the H-bond symmetrisation transition above 60 GPa4. Here, we used 1H-NMR on high-pressure ice up to 90 GPa, and demonstrate that NQEs govern the behavior of the hydrogen bonded protons in ice VII already at significantly lower pressures than previously expected. A pronounced tunneling mode was found to be present up to the highest pressures of 90 GPa, well into the stability field of ice X, where NQEs are not anticipated in a fully symmetrized H-bond network. We found two distinct transitions in the NMR shift data at about 20 GPa and 75 GPa attributed to the step-wise symmetrization of the H-bond (HB), with high-barrier H-Bonds (HBHB) to low-barrier H-bonds (LBHB) and LBHB to symmetric H-bonds (SHB) respectively. These transitions could have major implication on the physical properties of high-pressure ices and planetary interior models. NQEs observed in this chemically simple system over a wide pressure range could prove to be useful in designing a new generation of electronic devices exploiting protonic tunneling.

References in corpus (1)

• Magnetic Lenz lenses increase the limit-of-detection in nuclear magnetic resonance

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• Pressure induced Hydrogen-Hydrogen interaction in metallic FeH revealed by NMR
• In-situ High Pressure Nuclear Magnetic Resonance Crystallography
• Proton dynamics in high-pressure ice-VII from density functional theory
• Absence of proton tunneling during the hydrogen bond symmetrization in $\delta$-AlOOH
• Nuclear Spin Crossover in Dense Molecular Hydrogen
• Improving Resolution of Solid State NMR in Dense Molecular Hydrogen
• Table-top NMR system for high-pressure studies with in-situ laser heating
• Quantum Anharmonic Effects in Hydrogen-Bond Symmetrization of High-Pressure Ice
• A numerical study of the Bose-Einstein condensates in a double-well trap using finite differences