Hydrated Excess Protons in Acetonitrile/Water Mixtures - Solvation Species and Ultrafast Proton Motions

Abstract

The solvation structure of protons in aqueous media is highly relevant to electric properties and to proton transport in liquids and membranes. At ambient temperature, polar liquids display structural fluctuations on femto- to picosecond time scales with a direct impact on proton solvation. We apply two-dimensional infrared (2D-IR) spectroscopy for following proton dynamics in acetonitrile/water mixtures with the Zundel cation H${}_5$O${}_2^{+}$ prepared in neat acetonitrile as a benchmark. The 2D-IR spectra of the proton transfer mode of H${}_5$O${}_2^{+}$ demonstrate stochastic large-amplitude motions in the double-minimum proton potential, driven by fluctuating electric fields. In all cases the excess proton is embedded in a water dimer, forming an H${}_5$O${}_2^{+}$ complex as major solvation species. This observation is rationalized by quantum mechanics/molecular mechanics molecular dynamics simulations including up to 4 water molecules embedded in acetonitrile. The Zundel motif interacts with its closest water neighbor in an H${}_7$O${}_3^{+}$ unit without persistent proton localization.

References in corpus (1)

• Full dimensional (15D) quantum-dynamical simulation of the protonated water-dimer II: infrared spectrum and vibrational dynamics

Cited by in corpus (4)

• The coupling of the hydrated proton to its first solvation shell
• Infrared and NMR Spectroscopic Fingerprints of the Asymmetric H7+O3 Complex in Solution
• Proton-transfer spectroscopy beyond the normal-mode scenario
• Spectral signatures of excess-proton waiting and transfer-path dynamics in aqueous hydrochloric acid solutions