Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water.

ABSTRACT: The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381 °C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as the water monomer becomes electronically perturbed. Fits to the supercritical wate

SUBMITTER: Marin TW 

PROVIDER: S-EPMC5442368 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature