Picosecond Proton Transfer Kinetics in Water Revealed with Ultrafast IR Spectroscopy

Aqueous proton transport involves the ultrafast interconversion of hydrated proton species that are closely linked to the hydrogen bond dynamics of water, which has been a long-standing challenge to experiments. In this study, we use ultrafast IR spectroscopy to investigate the distinct vibrational transition centered at 1750 cm -1 in strong acid solutions, which arises from bending vibrations of the hydrated proton complex. Broadband ultrafast two-dimensional IR spectroscopy and transient absorption are used to measure vibrational relaxation, spectral diffusion, and orientational relaxation dynamics. The hydrated proton bend displays fast vibrational relaxation and spectral diffusion timescales of 200-300 fs; however, the transient absorption anisotropy decays on a remarkably long 2.5 ps timescale, which matches the timescale for hydrogen bond reorganization in liquid water. These observations are indications that the bending vibration of the aqueous proton complex is relatively localized, with an orientation that is insensitive to fast hydrogen bonding fluctuations and dependent on collective structural relaxation of the liquid to reorient. We conclude that the orientational relaxation is a result of proton transfer between configurations that are well described by a Zundel-like proton shared between two flanking water molecules.