The dipole moment of supercritical water - local vs. mean-field polarisation contributions

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MacPherson, Zoe and Gomes, José R. B. and Jorge, Miguel and Lue, Leo (2024) The dipole moment of supercritical water - local vs. mean-field polarisation contributions. Molecular Physics. pp. 1-13. e2381574. ISSN 0026-8976 (https://doi.org/10.1080/00268976.2024.2381574)

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Abstract

Supercritical water has attracted much attention from both fundamental and technological perspectives, based largely on its ability to solvate other molecules. Predicting and controlling this requires a deeper understanding of water's polarisation behaviour. Using the computationally efficient Self-Consistent Electrostatic Embedding method, we were able to calculate the water dipole moment over an unprecedented range of thermodynamic conditions, covering gas, liquid and supercritical states, with large simulation systems and a high-level quantum mechanical method. We find a discontinuous change in the dipole moment along subcritical isotherms, corresponding to the sharp transition between the vapour and liquid states, with the latter exhibiting induced dipole moments between 0.5 and 0.9 D, depending on the temperature. In contrast, the dipole moment changes continuously from gas-like to liquid-like behaviour in the supercritical regime, allowing the degree of polarisation to be controlled through manipulating temperature and pressure. The dipole moment was found to be linearly related to the average number of hydrogen-bonded neighbours of water, emphasising the key role of local interactions to the polarisation process. Mean-field approaches based on a dielectric continuum representation of the solvent are unable to predict this behaviour due to the neglect of local interactions.

ORCID iDs

MacPherson, Zoe, Gomes, José R. B., Jorge, Miguel ORCID logoORCID: https://orcid.org/0000-0003-3009-4725 and Lue, Leo ORCID logoORCID: https://orcid.org/0000-0002-4826-5337;
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