The microscopic origin of the anomalous isotopic properties of ice relies on the strong quantum anharmonic regime of atomic vibration.

Abstract

Water ice is a unique material presenting intriguing physical properties, such as negative thermal expansion and anomalous volume isotope effect (VIE). They arise from the interplay between weak hydrogen bonds and nuclear quantum fluctuations, making theoretical calculations challenging. Here, we employ the stochastic self-consistent harmonic approximation to investigate how thermal and quantum fluctuations affect the physical properties of ice XI with ab initio accuracy. Regarding the anomalous VIE, our work reveals that quantum effects on hydrogen are so strong to be in a nonlinear regime: When progressively increasing the mass of hydrogen from protium to infinity (classical limit), the volume first expands and then contracts, with a maximum slightly above the mass of tritium. We observe an anharmonic renormalization of about 10% in the bending and stretching phonon frequencies probed in IR and Raman experiments. For the first time, we report an accurate comparison of the low-energy phonon dispersion with the experimental data, possible only thanks to high-level accuracy in the electronic correlation and nuclear quantum and thermal fluctuations, paving the way for the study of thermal transport in ice from first-principles and the simulation of ice under pressure.