Phonons and Anomalous Thermal Expansion Behaviour of H2O and D2O ice Ih

Abstract

In order to identify and quantitatively analyze the anharmonicity of phonons relevant to the anomalous thermal expansion in the Ih phase of ice, we performed neutron inelastic scattering measurements of the phonon spectrum as a function of pressure up to 1 kbar at 225 K in deuterated ice (D2O), and as a function of temperature over 10-225 K at ambient pressure in both H2O and D2O ice. We also performed density functional theory calculations of the lattice dynamics. The anomalous expansion is quantitatively reproduced from the analysis of the neutron data as well as from the ab-initio calculations. Further, the ab-initio calculations are used to visualize the nature of anharmonic phonons across a large part of the Brillouin zone. We find that the negative thermal expansion below 60 K in the hexagonal plane is due to anharmonic librational motion of the hexagonal rings of the ice molecules, and that along the hexagonal axis originates from the transverse vibrations of the hexagonal layers.

arXiv comment5 Pages, 5 Figures, 1 Table and Supplementary materials

References in corpus (11)

• Van der Waals Density Functional for General Geometries
• Structural transformation in supercooled water controls the crystallization rate of ice
• Anomalous Nuclear Quantum Effects in Ice
• Pressure and stress tensor of complex anharmonic crystals within the stochastic self-consistent harmonic approximation
• On the nature of amorphous polymorphism of water
• Anharmonic nuclear motion and the relative stability of hexagonal and cubic ice
• Dielectric Anomaly in Ice near 20 K; Evidence of Macroscopic Quantum Phenomena
• Anomalous Thermal Expansion, Negative Linear Compressibility and High-Pressure Phase Transition in ZnAu2(CN)4: Neutron Inelastic Scattering and Lattice Dynamics Studies
• Electronic and Nuclear Quantum Effects on the Ice XI/Ice Ih Phase Transition
• Vibrational renormalisation of the electronic band gap in hexagonal and cubic ice
• Oxygen disorder in ice probed by X-ray Compton scattering

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