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

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