Broadband 2D IR spectroscopy reveals dominant asymmetric H5O2+ 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 H 5 O 2 + 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. Although ubiquitous throughout chemistry and biology, the structure and transport mechanism of the aqueous proton in solution remain elusive. Through advances in ultrafast broadband 2D IR spectroscopy, the structure of the aqueous proton is revealed to have a charge-delocalized H 5 O 2 + Zundel-like core arrangement with surprisingly persistent structural heterogeneity.