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

TL;DR

This study provides experimental evidence of nuclear quantum effects and hydrogen bond symmetrisation in high-pressure ice up to 90 GPa, revealing step-wise transitions and proton tunneling phenomena at pressures lower than previously predicted.

Contribution

First experimental observation of nuclear quantum effects and hydrogen bond symmetrisation in high-pressure ice using 1H-NMR up to 90 GPa, challenging prior theoretical predictions.

Findings

Proton tunneling observed up to 90 GPa.

Two distinct H-bond symmetrisation transitions at ~20 GPa and ~75 GPa.

NQEs influence hydrogen bonding behavior over a wide pressure range.

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.