Abstract
Mixed quantum-classical methods are commonly used to calculate infrared spectra for condensed-phase systems. These methods have been applied to study water in a range of conditions from liquid to solid to supercooled. Here, we show that these methods also predict infrared line shapes in excellent agreement with experiments in supercritical water. Specifically, we study the OD stretching mode of dilute HOD in H2O. We find no qualitative change in the spectrum upon passing through the near-critical region (Widom line) or the hydrogen-bond percolation line. At very low densities, the spectrum does change qualitatively, becoming rovibrational in character. We describe this rovibrational spectrum from the perspective of classical mechanics and provide a classical interpretation of the rovibrational line shape for both HOD and H2O. This treatment is perhaps more accessible than the conventional quantum-mechanical treatment.
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