Quantification of distortion of the water OH-band using picosecond Raman spectroscopy

Abstract

An anomalously large (~40 cm−1) blue-shift of the Raman OH stretching vibration band was observed when bulk water was probed by picosecond versus nanosecond pulses. The temperature distortion of the OH band contour (3200–3600 cm−1) was studied by both nanosecond and picosecond Raman techniques. It was observed that the OH band centroid shifted linearly with temperature (~0.87 cm−1 °C−1) for both nano- and picosecond pulses. This feature of the picosecond Raman spectra was explained by the dynamics of the non-equilibrium hydrogen bond structures in water.