Revealing excess protons in the infrared spectrum of liquid water

Abstract: The most common species in liquid water, next to neutral H$_2$O molecules, are the H$_3$O$^+$ and OH$^-$ ions. In a dynamic picture, their exact concentrations depend on the time scale at which these are probed. Here, using a spectral-weight analysis, we experimentally resolve the fingerprints of the elusive fluctuations-born short-living 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 find that short-living ions, with concentrations reaching $\sim 2\%$ of the content of water molecules, coexist with long-living pH-active ions on the picosecond timescale, thus making liquid water an effective ionic liquid in femtochemistry.