Hydrogen Dynamics in Supercritical Water Probed by Neutron Scattering and Computer Simulations

C Andreani and G Romanelli and A Parmentier and R Senesi and AI Kolesnikov and HY Ko and MFC Andrade and R Car, JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 11, 9461-9467 (2020).

DOI: 10.1021/acs.jpclett.0c02547

In this work, an investigation of supercritical water is presented combining inelastic and deep inelastic neutron scattering experiments and molecular dynamics simulations based on a machine-learned potential of ab initio quality. The local hydrogen dynamics is investigated at 250 bar and in the temperature range of 553-823 K, covering the evolution from subcritical liquid to supercritical gas-like water. The evolution of libration, bending, and stretching motions in the vibrational density of states is studied, analyzing the spectral features by a mode decomposition. Moreover, the hydrogen nuclear momentum distribution is measured, and its anisotropy is probed experimentally. It is shown that hydrogen bonds survive up to the higher temperatures investigated, and we discuss our results in the framework of the coupling between intramolecular modes and intermolecular librations. Results show that the local potential affecting hydrogen becomes less anisotropic within the molecular plane in the supercritical phase, and we attribute this result to the presence of more distorted hydrogen bonds.

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