Excess protons revealed in the infrared spectrum of liquid water

The most common species in liquid water, next to neutral H$_2$O molecules, are the H$_3$O$^+$ and OH$^-$ ions. Though they contribute to the infrared (IR) spectrum, they remain hidden within the broad absoption lines of neutral molecules. This severely hinders the interpretation of the spectroscopic data. Using a spectral-weight analysis, here we experimentally resolve the fingerprints of H$_3$O$^*$, DH$_2$O$^*$, HD$_2$O$^*$, and D$_3$O$^*$ ions in the IR spectra of light (H$_2$O), heavy (D$_2$O), and semi-heavy (HDO) water. We calculate the normal vibration modes of these ions, assign them to certain spectral features, and determine the ion concentrations. We find that the fluctuations-born short-living ions with a concentration of about two percent of the content of water molecules, coexist with long-living pH-active ions. We conclude that water is a "two-percent ionic liquid" at least on timescale shorter than picoseconds.