Quantum Anharmonic Effects in Hydrogen-Bond Symmetrization of High-Pressure Ice

TL;DR

This study investigates how nuclear quantum effects influence hydrogen-bond symmetrization in high-pressure ice, revealing the importance of anharmonicity and functional choice in accurately predicting transition pressures.

Contribution

It introduces neural canonical transformation to account for quantum anharmonicity, improving predictions of phase transition pressures in high-pressure ice.

Findings

Quantum fluctuations lower the transition pressure from 100 GPa to 60 GPa.

The PBE functional underestimates the hydrogen double-well barrier compared to more accurate functionals.

NCT reveals pressure-independent transition pressure and hydrogen bond softening in ice VIII.

Abstract

The nuclear quantum effects of hydrogen play a significant role in determining the phase stability of water ice. Hydrogen-bond symmetrization occurs as hydrogen atoms tunnel in a double-well potential, ultimately occupying the midpoint between oxygen atoms and transforming ice VIII into ice X under high pressure. Quantum fluctuations lower this transition from classical predictions of over 100 GPa to 60 GPa. We reveal that the Perdew-Burke-Ernzerhof functional underestimates the hydrogen double-well barrier, thus resulting in a transition pressure over 10 GPa lower than the strongly constrained and appropriately normed functional, which is validated against quantum Monte Carlo calculations. Nuclear quantum anharmonicity, treated via neural canonical transformation (NCT), reveals that this transition pressure is temperature-independent and observes a 2 GPa reduction when comparing the non-Gaussian flow models based wavefunction compared to the self-consistent harmonic approximation. Despite increasing pressure typically shortens chemical bonds and hardens phonon modes, NCT calculations reveal that hydrogen bond softens hydrogen-oxygen stretching in ice VIII upon pressure.