Hyper‐Raman study of hydrated excess protons in water: Measurement of concentrated HCl solution

We report hyper‐Raman (HR) spectra of concentrated hydrochloric acid solutions for the first time. HR signals from the OH stretching region to the low‐frequency region reflect the presence of chloride anions solvated in water. By contrast, it turns out that HR spectroscopy is insensitive to the presence of excess protons in water. HR spectra of HCl solutions do not show any signature of a proton continuum and shoulders on the high/low‐frequency sides of the bending mode of H2O in stark contrast to IR spectroscopy. Moreover, we found that a sharp HR signal around 500 cm−1 appear in 532 nm excited HR spectra. A laser power dependence indicates that this signal comes from a photochemical reaction. The absence of this signal under 1064 nm HR excitation and 532 nm Raman excitation suggests that the resonance (hyper‐)Raman effect enhances the signal from the photoproduct.