Broadband 2D IR spectroscopy reveals dominant asymmetric H 5 O 2 + proton hydration structures in acid solutions.

Given the critical role of the aqueous excess proton in redox chemistry, determining its structure and the mechanism of its transport in water are intense areas of experimental and theoretical research. The ultrafast dynamics of the proton's hydration structure has made it extremely challenging to study experimentally. Using ultrafast broadband two-dimensional infrared spectroscopy, we show that the vibrational spectrum of the aqueous proton is fully consistent with a protonated water complex broadly defined as a Zundel-like H5 O2 + motif. Analysis of the inhomogeneously broadened proton stretch two-dimensional lineshape indicates an intrinsically asymmetric, low-barrier O-H+ -O potential that exhibits surprisingly persistent distributions in both its asymmetry and O-O distance. This structural characterization has direct implications for the extent of delocalization exhibited by a proton's excess charge and for the possible mechanisms of proton transport in water.