  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.
